Volume39: Sulfur,Selenium,andTellurium · 2020. 7. 14. · 39.17 ProductClass17:AcyclicDialkylSelenoxidesandDerivatives T. Shimizu and N. Kamigata .....929 39.18 ProductClass18:Alkaneselenols

Volume 39:Sulfur, Selenium, and Tellurium

Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . V

Table of Contents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . XIII

IntroductionN. Kambe . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

39.1 Product Class 1: Alkanesulfonic Acids and Acyclic DerivativesJ. Drabowicz, P. Kiełbasinski, P. Łyzwa, A. Zajac, and M. Mikołajczyk . . . . . . . . . . 17

39.2 Product Class 2: Acyclic Dialkyl Sulfones and DerivativesJ. Drabowicz, J. Lewkowski, W. Kudelska, and T. Girek . . . . . . . . . . . . . . . . . . . . . . . 123

39.3 Product Class 3: Alkanesulfinic Acids and Acyclic DerivativesS. Braverman, M. Cherkinsky, and S. Levinger . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187

39.4 Product Class 4: Acyclic Dialkyl Sulfoxides and DerivativesJ. L. Garc4a Ruano, M. B. Cid, A. M. Mart4n-Castro, and J. Alem8n . . . . . . . . . . . . . 245

39.5 Product Class 5: AlkanethiolsJ. V. Comasseto and A. S. Guarezemini . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391

39.6 Product Class 6: Acyclic Alkanethiolates

39.6.1 Product Subclass 1: Alkanethiolates of Group 1, 2, and 13–15 MetalsJ. V. Comasseto and A. S. Guarezemini . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 413

39.6.2 Product Subclass 2: Alkanethiolates of Group 3–12 MetalsA. Polo and J. Real . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 437

39.7 Product Class 7: Acyclic Dialkyl SulfidesS. Fujiwara and M. Toyofuku . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 469

39.8 Product Class 8: Acyclic Trialkyloxosulfonium and Trialkylsulfonium Saltsand DerivativesY. Tang and X.-L. Sun . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 501

39.9 Product Class 9: Alkanesulfenic Acids and Acyclic DerivativesJ. Drabowicz, P. Kiełbasinski, P. Łyzwa, and M. Mikołajczyk . . . . . . . . . . . . . . . . . . 543

39.10 Product Class 10: Acyclic Di- and PolysulfidesR. Sato and T. Kimura . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 573

39.11 Product Class 11: Thiiranes and DerivativesM. Saito and J. Nakayama . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 589

39.12 Product Class 12: Thietanes, 1,2-Oxathietanes, and DerivativesE. Block . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 659

VII

Science of Synthesis Original Edition Volume 39 © Georg Thieme Verlag KG

39.12.1 Product Subclass 1: Thietanes and DerivativesE. Block . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 661

39.12.2 Product Subclass 2: 1,2-Oxathietanes and DerivativesJ. Drabowicz and J. Lewkowski . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 711

39.12.3 Product Subclass 3: 1,2-Dithietanes, 1,2-Thiazetidines,1,2-Thiaphosphetanes, and Derivatives of Various Oxidation StatesN. Kambe . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 727

39.13 Product Class 13: Thiolanes, Larger Rings, and Derivativesof Various Oxidation StatesR. Sato and T. Kimura . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 733

39.13.1 Product Subclass 1: Cyclic Alkanesulfonic Acid DerivativesR. Sato and T. Kimura . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 735

39.13.2 Product Subclass 2: Cyclic Dialkyl Sulfones and DerivativesR. Sato and T. Kimura . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 745

39.13.3 Product Subclass 3: Cyclic Alkanesulfinic Acid DerivativesR. Sato and T. Kimura . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 751

39.13.4 Product Subclass 4: Cyclic Dialkyl Sulfoxides and DerivativesJ. L. Garc4a-Ruano, M. B. Cid, A. M. Mart4n-Castro, and J. Alem8n . . . . . . . . . . . . 757

39.13.5 Product Subclass 5: Cyclic Alkanethiolates of Group 1, 2,and 13–15 MetalsN. Kambe . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 811

39.13.6 Product Subclass 6: Cyclic Alkanethiolates of Group 3–12 MetalsA. Polo and J. Real . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 813

39.13.7 Product Subclass 7: Cyclic Dialkyl SulfidesM. Segi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 833

39.13.8 Product Subclass 8: Cyclic Trialkyloxosulfonium andTrialkylsulfonium Salts and DerivativesY. Tang and X.-L. Sun . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 851

39.13.9 Product Subclass 9: Cyclic Alkanesulfenic Acid DerivativesT. Wirth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 879

39.13.10 Product Subclass 10: Cyclic Dialkyl Di- and PolysulfidesR. Sato and T. Kimura . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 885

39.14 Product Class 14: Alkaneselenonic Acids and Acyclic DerivativesJ. Drabowicz, P. Kiełbasinski, P. Łyzwa, and M. Mikołajczyk . . . . . . . . . . . . . . . . . . 903

39.15 Product Class 15: Acyclic Dialkyl Selenones and DerivativesJ. Drabowicz, J. Lewkowski, W. Kudelska, and T. Girek . . . . . . . . . . . . . . . . . . . . . . . 909

39.16 Product Class 16: Alkaneseleninic Acids and Acyclic DerivativesS. Braverman, M. Cherkinsky, and S. Levinger . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 915

VIII Overview


39.17 Product Class 17: Acyclic Dialkyl Selenoxides and DerivativesT. Shimizu and N. Kamigata . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 929

39.18 Product Class 18: AlkaneselenolsJ. V. Comasseto and A. S. Guarezemini . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 941

39.19 Product Class 19: Acyclic Alkaneselenolates

39.19.1 Product Subclass 1: Alkaneselenolates of Group 1, 2, and 13–15 MetalsJ. V. Comasseto and A. S. Guarezemini . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 947

39.19.2 Product Subclass 2: Alkaneselenolates of Group 3–12 MetalsA. Polo and J. Real . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 961

39.20 Product Class 20: Acyclic Dialkyl SelenidesM. Segi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 977

39.21 Product Class 21: Acyclic Trialkylselenonium Salts and DerivativesY. Tang and X.-L. Sun . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 995

39.22 Product Class 22: Alkaneselenenic Acids and Acyclic DerivativesT. Wirth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1005

39.23 Product Class 23: Acyclic Di- and PolyselenidesR. Sato and T. Kimura . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1013

39.24 Product Class 24: Seleniranes and DerivativesM. Saito and J. Nakayama . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1023

39.25 Product Class 25: Selenetanes and DerivativesE. Block . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1033

39.26 Product Class 26: Selenolanes, Larger Rings, and Derivativesof Various Oxidation StatesR. Sato and T. Kimura . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1043

39.26.1 Product Subclass 1: Cyclic Alkaneselenonic Acid DerivativesR. Sato and T. Kimura . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1045

39.26.2 Product Subclass 2: Cyclic Dialkyl Selenones and DerivativesR. Sato and T. Kimura . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1047

39.26.3 Product Subclass 3: Cyclic Alkaneseleninic Acid DerivativesR. Sato and T. Kimura . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1049

39.26.4 Product Subclass 4: Cyclic Dialkyl Selenoxides and DerivativesT. Shimizu and N. Kamigata . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1053

39.26.5 Product Subclass 5: Cyclic Alkaneselenolates of Group 1, 2,and 13–15 MetalsN. Kambe . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1059

39.26.6 Product Subclass 6: Cyclic Alkaneselenolates of Group 3–12 MetalsA. Polo and J. Real . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1063

Overview IX


39.26.7 Product Subclass 7: Cyclic Dialkyl SelenidesM. Segi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1069

39.26.8 Product Subclass 8: Cyclic Trialkylselenonium Salts and DerivativesY. Tang and X.-L. Sun . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1083

39.26.9 Product Subclass 9: Cyclic Alkaneselenenic Acid DerivativesT. Wirth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1093

39.26.10 Product Subclass 10: Cyclic Dialkyl Di- and PolyselenidesR. Sato and T. Kimura . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1097

39.27 Product Class 27: Alkanetelluronic Acids and Acyclic DerivativesJ. Drabowicz, P. Kiełbasinski, P. Łyzwa, and M. Mikołajczyk . . . . . . . . . . . . . . . . . 1109

39.28 Product Class 28: Acyclic Dialkyl Tellurones and DerivativesJ. Drabowicz, J. Lewkowski, W. Kudelska, and T. Girek . . . . . . . . . . . . . . . . . . . . . . 1111

39.29 Product Class 29: Alkanetellurinic Acids and Acyclic DerivativesS. Braverman, M. Cherkinsky, and S. Levinger . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1117

39.30 Product Class 30: Acyclic Dialkyl Telluroxides and DerivativesT. Shimizu and N. Kamigata . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1127

39.31 Product Class 31: AlkanetellurolsJ. V. Comasseto and A. S. Guarezemini . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1137

39.32 Product Class 32: Acyclic Alkanetellurolates

39.32.1 Product Subclass 1: Alkanetellurolates of Group 1, 2, and 13–15 MetalsJ. V. Comasseto and A. S. Guarezemini . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1139

39.32.2 Product Subclass 2: Alkanetellurolates of Group 3–12 MetalsA. Polo and J. Real . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1145

39.33 Product Class 33: Acyclic Dialkyl TelluridesM. Segi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1163

39.34 Product Class 34: Acyclic Trialkyltelluronium Salts and DerivativesY. Tang and X.-L. Sun . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1179

39.35 Product Class 35: Alkanetellurenic Acids and Acyclic DerivativesT. Wirth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1193

39.36 Product Class 36: Acyclic Di- and PolytelluridesR. Sato and T. Kimura . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1197

39.37 Product Class 37: Telluriranes and DerivativesM. Saito and J. Nakayama . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1203

39.38 Product Class 38: Telluretanes and DerivativesE. Block . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1205

X Overview


39.39 Product Class 39: Tellurolanes, Larger Rings, and Derivativesof Various Oxidation StatesR. Sato and T. Kimura . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1207

39.39.1 Product Subclass 1: Cyclic Alkanetelluronic Acid DerivativesR. Sato and T. Kimura . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1209

39.39.2 Product Subclass 2: Cyclic Dialkyl Tellurones and DerivativesR. Sato and T. Kimura . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1211

39.39.3 Product Subclass 3: Cyclic Alkanetellurinic Acid DerivativesR. Sato and T. Kimura . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1213

39.39.4 Product Subclass 4: Cyclic Dialkyl Telluroxides and DerivativesT. Shimizu and N. Kamigata . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1215

39.39.5 Product Subclass 5: Cyclic Alkanetellurolates of Group 1, 2,and 13–15 MetalsN. Kambe . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1217

39.39.6 Product Subclass 6: Cyclic Alkanetellurolates of Group 3–12 MetalsA. Polo and J. Real . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1219

39.39.7 Product Subclass 7: Cyclic Dialkyl TelluridesM. Segi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1225

39.39.8 Product Subclass 8: Cyclic Trialkyltelluronium Salts and DerivativesY. Tang and X.-L. Sun . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1233

39.39.9 Product Subclass 9: Cyclic Alkanetellurenic Acid DerivativesT. Wirth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1243

39.39.10 Product Subclass 10: Cyclic Dialkyl Di- and PolytelluridesR. Sato and T. Kimura . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1245

Keyword Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1251

Author Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1317

Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1379

Overview XI


XII


Table of Contents

IntroductionN. Kambe

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

39.1 Product Class 1: Alkanesulfonic Acids and Acyclic DerivativesJ. Drabowicz, P. Kiełbasinski, P. Łyzwa, A. Zajac, and M. Mikołajczyk

39.1 Product Class 1: Alkanesulfonic Acids and Acyclic Derivatives . . . . . . . . . . . . . 17

39.1.1 Product Subclass 1: Alkylsulfur Pentahalides (Alkylpentahalo-l6-sulfanes) 18

39.1.1.1 Synthesis of Product Subclass 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

39.1.1.1.1 Method 1: Additions to Methylenesulfur Tetrafluoride . . . . . . . . . . . . . . . . . . . 1839.1.1.1.2 Method 2: Addition of Sulfur Pentafluoride Halides to Alkenes . . . . . . . . . . . 19

39.1.2 Product Subclass 2: Alkanesulfonyl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19


39.1.2.1.1 Method 1: Sulfochlorination Reactions: Formation of the C—S Bond . . . . . . 2039.1.2.1.1.1 Variation 1: Reaction of Alkanes with Chlorine and Sulfur Dioxide or Trioxide 2039.1.2.1.1.2 Variation 2: Reaction of Organometallic Reagents with Sulfuryl Chloride . . 2039.1.2.1.1.3 Variation 3: Addition of Sulfuryl Chloride or Fluoride to Alkenes . . . . . . . . . . . 2139.1.2.1.1.4 Variation 4: Reaction of Alkenes with Thioacetic Acid and Chlorine . . . . . . . . 2239.1.2.1.2 Method 2: Synthesis from Sulfinic Acid Derivatives . . . . . . . . . . . . . . . . . . . . . . 2239.1.2.1.2.1 Variation 1: Oxidation of Sulfinic Acids or Their Salts with Halogens or

Halogen-Containing Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2239.1.2.1.2.2 Variation 2: Oxidative Halogenation of Magnesium Alkanesulfinates

formed In Situ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2439.1.2.1.2.3 Variation 3: Oxidative Chlorination of Sulfinic Acid Esters . . . . . . . . . . . . . . . . . 2439.1.2.1.3 Method 3: Synthesis from Divalent Organosulfur Derivatives . . . . . . . . . . . . 2539.1.2.1.3.1 Variation 1: Oxidation of Thiols or Disulfides with Halogens . . . . . . . . . . . . . . . 2539.1.2.1.3.2 Variation 2: Reaction of S-Alkylisothiuronium Salts with Chlorine in

Aqueous Solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2639.1.2.1.3.3 Variation 3: Reaction of Sulfides with Chlorine in Aqueous Solution . . . . . . . 2739.1.2.1.3.4 Variation 4: Oxidation of Sulfenyl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2939.1.2.1.3.5 Variation 5: Reaction of Thiocyanates with Chlorine in Aqueous Solution . . 2939.1.2.1.3.6 Variation 6: Oxidative Chlorination of Thioesters . . . . . . . . . . . . . . . . . . . . . . . . . 2939.1.2.1.3.7 Variation 7: Chlorolysis of Bunte Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3039.1.2.1.4 Method 4: Synthesis from Sulfonic Acids and Their Salts . . . . . . . . . . . . . . . . . 3039.1.2.1.4.1 Variation 1: Reaction of Sulfonic Acids and Their Salts with Phosphorus

Pentachloride or Pentabromide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3139.1.2.1.4.2 Variation 2: Reaction with Phosphoryl Chloride . . . . . . . . . . . . . . . . . . . . . . . . . . 3239.1.2.1.4.3 Variation 3: Reaction with Thionyl Chloride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3239.1.2.1.4.4 Variation 4: Reaction with Sulfuryl Chloride/Triphenylphosphine . . . . . . . . . . 3339.1.2.1.4.5 Variation 5: Reaction with Dichloromethyl Methyl Ether . . . . . . . . . . . . . . . . . . 3539.1.2.1.5 Method 5: Synthesis from Sulfonic Anhydrides . . . . . . . . . . . . . . . . . . . . . . . . . . 35

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39.1.2.1.6 Method 6: Ring Opening of Fluoro-1,2-oxathietane 2,2-Dioxides . . . . . . . . . 3539.1.2.1.7 Method 7: Synthesis from Sulfonyl Halides by Halide Ion Exchange . . . . . . . 3639.1.2.1.8 Methods 8: Miscellaneous Approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37

39.1.3 Product Subclass 3: Alkanesulfonic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38


39.1.3.1.1 Method 1: Direct Sulfonation of Hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . 3939.1.3.1.1.1 Variation 1: Reaction of Alkanes with Sulfuric Acid, Sulfur Trioxide, and

Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3939.1.3.1.1.2 Variation 2: Reaction of Alkanes with Sulfur Dioxide and Oxygen . . . . . . . . . . 3939.1.3.1.1.3 Variation 3: Reactions between Unsaturated Hydrocarbons and Sulfuric

Acid or Its Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4039.1.3.1.1.4 Variation 4: Reaction of Alkenes with the Hydrogen Sulfite Ion . . . . . . . . . . . . 4139.1.3.1.1.5 Variation 5: Photosensitized Reactions between Alkenes and Sulfur Dioxide 4139.1.3.1.1.6 Variation 6: Palladium-Catalyzed Additions of Sulfur Dioxide to Alkenes . . . 4239.1.3.1.2 Method 2: Oxidation of Low-Valency Sulfur Derivatives . . . . . . . . . . . . . . . . . . 4239.1.3.1.2.1 Variation 1: Oxidation of Thiols and Their Derivatives . . . . . . . . . . . . . . . . . . . . . 4239.1.3.1.2.2 Variation 2: Oxidation of Sulfinic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4339.1.3.1.3 Method 3: Reaction of Organometallic Reagents with Sulfur Trioxide

Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4439.1.3.1.4 Method 4: Interconversions of Other Sulfonyl Derivatives . . . . . . . . . . . . . . . 4439.1.3.1.4.1 Variation 1: Hydrolysis of Sulfonyl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4439.1.3.1.4.2 Variation 2: Hydrolysis of Sulfonic Acid Esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4539.1.3.1.4.3 Variation 3: Ring Opening of Cyclic Sulfonates (Sultones) . . . . . . . . . . . . . . . . . 4539.1.3.1.4.4 Variation 4: Cleavage of Alkyl Perfluoroalkyl Sulfones . . . . . . . . . . . . . . . . . . . . . 4639.1.3.1.5 Method 5: Nucleophilic Substitution with Sulfite Anions . . . . . . . . . . . . . . . . . 4639.1.3.1.5.1 Variation 1: Reaction of Haloalkanes with Inorganic Sulfites . . . . . . . . . . . . . . 4639.1.3.1.5.2 Variation 2: Reaction of Alkyl Sulfates and Sulfonates with Inorganic Sulfites 4739.1.3.1.5.3 Variation 3: Ring Opening of Oxiranes and Aziridines with Sulfite Anions . . 48

39.1.3.2 Applications of Product Subclass 3 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . . . 48

39.1.3.2.1 Method 1: Alkanesulfonic Acids as Catalysts for Condensation Reactions . 48

39.1.4 Product Subclass 4: Alkanesulfonic Acid Esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49


39.1.4.1.1 Method 1: Synthesis from Sulfonic Acids and Their Salts . . . . . . . . . . . . . . . . . 4939.1.4.1.1.1 Variation 1: Direct Esterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4939.1.4.1.1.2 Variation 2: Alkylation of a Sulfonate Anion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5039.1.4.1.2 Method 2: Synthesis from Sulfonyl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5039.1.4.1.3 Method 3: Synthesis from Sulfonic Anhydrides . . . . . . . . . . . . . . . . . . . . . . . . . . 5139.1.4.1.4 Method 4: Synthesis from Sulfonamides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5239.1.4.1.5 Method 5: Synthesis from Diazo Compounds and Sulfur Dioxide . . . . . . . . . 5339.1.4.1.6 Method 6: Synthesis from Sulfenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5339.1.4.1.7 Method 7: Synthesis from Sulfenate and Sulfinate Esters . . . . . . . . . . . . . . . . 5339.1.4.1.8 Method 8: Rearrangement of Sulfites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5439.1.4.1.8.1 Variation 1: [2,3]-Sigmatropic Rearrangements of Allyl Sulfites . . . . . . . . . . . 5439.1.4.1.8.2 Variation 2: Rearrangements of Dialkyl Sulfites . . . . . . . . . . . . . . . . . . . . . . . . . . 54

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39.1.4.1.9 Method 9: Synthesis from Alkenes and Sulfur Trioxide or Other SulfuricAcid Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54

39.1.4.1.10 Method 10: Synthesis from Other Sulfonyl Derivatives . . . . . . . . . . . . . . . . . . . . 5539.1.4.1.10.1 Variation 1: From Unsaturated Sulfonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5539.1.4.1.10.2 Variation 2: By the Decarboxylation of (Alkoxysulfonyl)acetates . . . . . . . . . . . 5639.1.4.1.10.3 Variation 3: By the Functionalization of the S-Alkyl Group of Alkanesulfonic

Acid Esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56

39.1.4.2 Applications of Product Subclass 4 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . . . 56

39.1.4.2.1 Method 1: Use as Alkylating Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5639.1.4.2.1.1 Variation 1: Reactions with Nitrogen Nucleophiles . . . . . . . . . . . . . . . . . . . . . . . 5639.1.4.2.1.2 Variation 2: Reactions with Oxygen Nucleophiles . . . . . . . . . . . . . . . . . . . . . . . . . 5739.1.4.2.1.3 Variation 3: Methylation at Sulfur or Selenium . . . . . . . . . . . . . . . . . . . . . . . . . . . 5739.1.4.2.1.4 Variation 4: Methylation of Organophosphorus Compounds . . . . . . . . . . . . . . 57

39.1.5 Product Subclass 5: Alkanesulfonic Anhydrides . . . . . . . . . . . . . . . . . . . . . . . . . . . 58


39.1.5.1.1 Method 1: Synthesis of Symmetrical and Unsymmetrical Anhydrides ofAlkanesulfonic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58

39.1.5.1.2 Method 2: Synthesis of Mixed Anhydrides of Carboxylic andAlkanesulfonic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58

39.1.5.1.2.1 Variation 1: Reaction of Carboxylic (Carbonic) Acids or Their Anions withAlkanesulfonyl Chlorides or Related Compounds . . . . . . . . . . . . . 58

39.1.5.1.2.2 Variation 2: Reaction of Carboxylic Acid Chlorides with AlkanesulfonicAcids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60

39.1.5.1.2.3 Variation 3: Reaction of Trimethylsilyl Alkanesulfonates withTrifluoroacetic Anhydride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60

39.1.5.1.3 Method 3: Synthesis of Mixed Anhydrides of Alkanesulfonic and OrganicAcids of Phosphorus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61

39.1.5.1.3.1 Variation 1: Reaction of Sulfonyl Derivatives with TrivalentOrganophosphorus Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61

39.1.5.1.3.2 Variation 2: Reaction of Sulfonyl Derivatives with PentavalentOrganophosphorus Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62

39.1.6 Product Subclass 6: Alkanethiosulfonic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63


39.1.6.1.1 Method 1: Synthesis from Sulfonyl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6339.1.6.1.2 Method 2: Reaction of Sulfur with Alkanesulfinates . . . . . . . . . . . . . . . . . . . . . 64

39.1.7 Product Subclass 7: S-Alkyl and S-Aryl Alkanethiosulfonates . . . . . . . . . . . . . . 65


39.1.7.1.1 Method 1: Synthesis from Sulfonyl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6539.1.7.1.1.1 Variation 1: By Reactions with Thiols or Thiolates . . . . . . . . . . . . . . . . . . . . . . . . 6539.1.7.1.1.2 Variation 2: Reductive Zinc Coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6739.1.7.1.2 Method 2: Synthesis from Sulfinyl Chlorides . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6839.1.7.1.2.1 Variation 1: Coupling Reactions Mediated by Carboxamides . . . . . . . . . . . . . . 6839.1.7.1.2.2 Variation 2: Coupling of Alkanesulfinyl Chlorides with Powdered Zinc . . . . . 6939.1.7.1.3 Method 3: Synthesis from Disulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6939.1.7.1.3.1 Variation 1: Oxidation with Hydrogen Peroxide . . . . . . . . . . . . . . . . . . . . . . . . . . 69

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39.1.7.1.3.2 Variation 2: Oxidation with Peroxy Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7039.1.7.1.3.3 Variation 3: Oxidation with Other Oxidizing Reagents . . . . . . . . . . . . . . . . . . . 7139.1.7.1.3.4 Variation 4: Reactions with Sulfenyl Chlorides Generated In Situ . . . . . . . . . 7239.1.7.1.3.5 Variation 5: Reactions with Sodium Methanesulfinate . . . . . . . . . . . . . . . . . . . 7239.1.7.1.4 Method 4: Reaction between Dimethyl Sulfoxide and

Chlorotrimethylsilane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7339.1.7.1.5 Method 5: Alkylation of the Salts of Alkanethiosulfonic Acids . . . . . . . . . . . 74

39.1.8 Product Subclass 8: Alkanesulfonamides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76

39.1.8.1 Synthesis of Product Subclass 8 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76

39.1.8.1.1 Method 1: Interconversion of Sulfonyl Derivatives . . . . . . . . . . . . . . . . . . . . . . 7639.1.8.1.1.1 Variation 1: Reaction of Isolated Sulfonyl Chlorides with Ammonia or

Amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7739.1.8.1.1.2 Variation 2: Reaction of In Situ Generated Sulfonyl Halides with Amines . . 8139.1.8.1.1.3 Variation 3: Reactions between the N-Chloroamine Salts of

Alkanesulfonamides and Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . 8239.1.8.1.1.4 Variation 4: Catalytic N-Sulfonylaziridination of Alkanes with Sulfonyl

Chlorides in the Presence of a Nitridomanganese Complex . . . 8439.1.8.1.1.5 Variation 5: Catalytic N-Sulfonylaziridination of Alkenes with an

N-Sulfonylimino(phenyl)-l3-iodane . . . . . . . . . . . . . . . . . . . . . . . . . 8539.1.8.1.1.6 Variation 6: Reaction of Allenes with N-[2-(Trimethylsilyl)ethanesulfo-

nyl]alkanimines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8739.1.8.1.1.7 Variation 7: Reactions between Benzotriazole Sulfonamides and Amines . 8739.1.8.1.1.8 Variation 8: Reaction of 1H-Benzotriazol-1-yl Methanesulfonate with

Primary Amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8839.1.8.1.1.9 Variation 9: Reduction of Sulfonyl Azides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8839.1.8.1.1.10 Variation 10: Reactions between Methylsulfamoyl Chloride and Silyl Enol

Ethers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8939.1.8.1.1.11 Variation 11: Cyclization of Alkanesulfonamides . . . . . . . . . . . . . . . . . . . . . . . . . . 9039.1.8.1.1.12 Variation 12: Reaction of Sulfonamide Anions with Epoxides . . . . . . . . . . . . . . 9239.1.8.1.1.13 Variation 13: Condensation of Alkanesulfonamides with Carboxylic Acids . . 9339.1.8.1.1.14 Variation 14: Reaction of Alkyl a-Disulfones with Amines . . . . . . . . . . . . . . . . . 9439.1.8.1.2 Method 2: Reaction of Sulfinyl Chloride with Hydroxylamines . . . . . . . . . . . 9439.1.8.1.3 Method 3: Reaction of Sulfur Dioxide with Diazo Compounds in the

Presence of Amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9539.1.8.1.4 Method 4: Oxidation of Low-Valency Sulfur Derivatives . . . . . . . . . . . . . . . . . 9539.1.8.1.4.1 Variation 1: Oxidation of Sulfenamides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9539.1.8.1.4.2 Variation 2: Oxidation of Sulfinamides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96

39.1.9 Product Subclass 9: Alkanesulfonohydrazides . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97


39.1.9.1.1 Method 1: Reaction of Alkanesulfinates with Azodicarboxylates . . . . . . . . 9739.1.9.1.2 Method 2: Reaction of Sulfonyl Chlorides with Hydrazine Derivatives . . . . 9839.1.9.1.3 Method 3: Oxidative Coupling of N-Substituted Methanesulfonamides . . 99

39.1.10 Product Subclass 10: N-Haloalkanesulfonamides and Their Salts . . . . . . . . . 100

39.1.10.1 Synthesis of Product Subclass 10 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100

39.1.10.1.1 Method 1: Halogenation of Alkanesulfonamides . . . . . . . . . . . . . . . . . . . . . . . 100

XVI Table of Contents


39.1.10.1.1.1 Variation 1: Chlorination with tert-Butyl Hypochlorite . . . . . . . . . . . . . . . . . . . 10039.1.10.1.1.2 Variation 2: Chlorination with Sodium Hypochlorite . . . . . . . . . . . . . . . . . . . . . 10139.1.10.1.1.3 Variation 3: Synthesis of N-Chloro- and N-Bromoperfluoroalkanesulfon-

amides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10139.1.10.1.1.4 Variation 4: Fluorination of N-Substituted Trifluoromethanesulfonamides 102

39.1.11 Product Subclass 11: Alkanesulfonyl N=C=X Derivatives . . . . . . . . . . . . . . . . . 102


39.1.11.1.1 Method 1: Synthesis of Alkanesulfonyl Isocyanates . . . . . . . . . . . . . . . . . . . . . 10239.1.11.1.1.1 Variation 1: From Alkanesulfonamides and Carbonyl Group Precursors . . . 10239.1.11.1.1.2 Variation 2: From Chlorosulfonyl Isocyanate and Alkenes . . . . . . . . . . . . . . . . 10339.1.11.1.1.3 Variation 3: By Thermolysis of Trimethylsilylated Alkanesulfonyl

Carbamates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10339.1.11.1.1.4 Variation 4: By Reactions between Chlorosulfonyl Isocyanate and

Tetraalkylstannanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10439.1.11.1.2 Method 2: Synthesis of Alkanesulfonyl Isothiocyanates . . . . . . . . . . . . . . . . . 104

39.1.12 Product Subclass 12: Alkanesulfonyl Azides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104


39.1.12.1.1 Method 1: Reaction of Alkanesulfonyl Halides with Alkali Metal Azidesor Tetramethylguanidinium Azide . . . . . . . . . . . . . . . . . . . . . . . . . . 104

39.1.13 Product Subclass 13: Alkanesulfonimidic Acid Derivatives . . . . . . . . . . . . . . . . 106


39.1.13.1.1 Method 1: Synthesis of Alkanesulfonimidoyl Halides . . . . . . . . . . . . . . . . . . . 10639.1.13.1.2 Method 2: Synthesis of Alkanesulfonimidic Acid Esters . . . . . . . . . . . . . . . . . 10939.1.13.1.3 Method 3: Synthesis of Alkanesulfonimidic Acid Amides . . . . . . . . . . . . . . . . 109

39.1.14 Product Subclass 14: Alkanesulfonodiimidic Acid Derivatives . . . . . . . . . . . . 111


39.1.14.1.1 Method 1: Synthesis of N,N¢,N¢¢-Trialkylalkanesulfonodiimidamides . . . . . 111

39.2 Product Class 2: Acyclic Dialkyl Sulfones and DerivativesJ. Drabowicz, J. Lewkowski, W. Kudelska, and T. Girek

39.2 Product Class 2: Acyclic Dialkyl Sulfones and Derivatives . . . . . . . . . . . . . . . . . 123

39.2.1 Product Subclass 1: Dialkylsulfur Tetrahalides . . . . . . . . . . . . . . . . . . . . . . . . . . . 123


39.2.1.1.1 Method 1: Reaction of Dialkyl Sulfides with Trifluoromethyl Hypofluoriteor Elemental Halogens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124

39.2.2 Product Subclass 2: Dialkyl Sulfones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124


39.2.2.1.1 Method 1: Alkylation of Sulfinic Acid Anions with Cleavage of a C—X orC—H Bond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125

39.2.2.1.1.1 Variation 1: Alkylation of Alkali Metal Salts under HomogeneousConditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125

Table of Contents XVII


39.2.2.1.1.2 Variation 2: Alkylation under Phase-Transfer Catalysis Conditions . . . . . . . . 12639.2.2.1.1.3 Variation 3: Alkylation in Ionic Liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12739.2.2.1.1.4 Variation 4: Dialkylation of the Sulfite Dianion . . . . . . . . . . . . . . . . . . . . . . . . . . 12739.2.2.1.1.5 Variation 5: Alkylation of Sulfinic Acid Anions Generated by

Electrochemical Oxidation of Disulfides . . . . . . . . . . . . . . . . . . . . . 12839.2.2.1.2 Method 2: Addition of Sulfinic Acids to Michael Acceptors . . . . . . . . . . . . . . 12839.2.2.1.3 Method 3: Reactions of Sulfonic Acid Derivatives . . . . . . . . . . . . . . . . . . . . . . 12939.2.2.1.3.1 Variation 1: Reaction of Sulfonyl Halides with Alkenes or Alkynes . . . . . . . . 12939.2.2.1.3.2 Variation 2: Free-Radical Reaction of Sulfonyl Halides with Unsaturated

Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13039.2.2.1.3.3 Variation 3: Reaction of Sulfonyl Halides with Organometallic Reagents . . 13139.2.2.1.3.4 Variation 4: Reaction of b-Sultones with Grignard Reagents . . . . . . . . . . . . . 13239.2.2.1.4 Method 4: Reactions of Sulfur Dioxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13239.2.2.1.4.1 Variation 1: Photochemical Reaction with Alkanes . . . . . . . . . . . . . . . . . . . . . . 13239.2.2.1.4.2 Variation 2: Four-Component Coupling with Silyl Enol Ethers, Dienes, and

Haloalkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13339.2.2.1.4.3 Variation 3: Reaction with Silyl Enol Ethers or Allylmetals . . . . . . . . . . . . . . . . 13539.2.2.1.5 Method 5: Oxidation of Sulfides or Sulfoxides . . . . . . . . . . . . . . . . . . . . . . . . . . 13539.2.2.1.5.1 Variation 1: Oxidation by Hydrogen Peroxide . . . . . . . . . . . . . . . . . . . . . . . . . . . 13539.2.2.1.5.2 Variation 2: Oxidation with Peroxy Acids and Other Peroxo Derivatives . . . 13639.2.2.1.5.3 Variation 3: Oxidation by Miscellaneous Oxidants . . . . . . . . . . . . . . . . . . . . . . . 13839.2.2.1.6 Method 6: Rearrangement of Sulfinic Acid Derivatives . . . . . . . . . . . . . . . . . . 13939.2.2.1.7 Method 7: Reactions of Oxo–Oxy Sulfonium Ylides . . . . . . . . . . . . . . . . . . . . . 14039.2.2.1.8 Method 8: Modification of the Alkyl Side Chains . . . . . . . . . . . . . . . . . . . . . . . 14139.2.2.1.8.1 Variation 1: Alkylation of the a-Carbanion of Sulfones . . . . . . . . . . . . . . . . . . . 14139.2.2.1.8.2 Variation 2: Radical Addition of Iodomethyl Sulfones to Alkenes or Alkynes 14239.2.2.1.8.3 Variation 3: Addition to Vinyl Sulfones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14339.2.2.1.8.4 Variation 4: Alkylation of Benzothiazolyl Sulfones . . . . . . . . . . . . . . . . . . . . . . . 14439.2.2.1.8.5 Variation 5: Alkylation at a Remote Group of the Side Chain of Sulfones . . 14539.2.2.1.8.6 Variation 6: Cross Coupling between a Haloalkyl Sulfone and an

Organoborane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14539.2.2.1.8.7 Variation 7: Condensation with Amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14539.2.2.1.8.8 Variation 8: Carbocycle Formation by Double Alkylation at the a-Carbon

of Sulfones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14639.2.2.1.8.9 Variation 9: Bromination of a Vinyl Sulfone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14639.2.2.1.8.10 Variation 10: Friedel–Crafts Arylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14739.2.2.1.8.11 Variation 11: Addition Reactions of Allenyl Sulfones . . . . . . . . . . . . . . . . . . . . . . 14739.2.2.1.8.12 Variation 12: Epoxidation of a Vinyl Sulfone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14739.2.2.1.8.13 Variation 13: Degradation of a Macrocyclic Sulfone . . . . . . . . . . . . . . . . . . . . . . . 14839.2.2.1.8.14 Variation 14: cis–trans Isomerization of 2-Isopropyl-5-mesyl-1,3-dioxane

or -dithiane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14839.2.2.1.8.15 Variation 15: Diels–Alder Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14839.2.2.1.8.16 Variation 16: Base-Catalyzed Rearrangement of a Polycycle-Substituted

Alkyl Sulfone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14939.2.2.1.8.17 Variation 17: Hydrolysis of Tetrachloro-1,3-dithietane 1,1,3,3-Tetraoxide . . 14939.2.2.1.8.18 Variation 18: Acylation of a-Sulfonyl Carbanions . . . . . . . . . . . . . . . . . . . . . . . . . 15039.2.2.1.8.19 Variation 19: Reaction of a-Sulfonyl Carbanions with Carbonyl Compounds 15039.2.2.1.8.20 Variation 20: Base-Catalyzed Elimination Reaction of b-Hydroxy Sulfones . . 151

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39.2.2.1.8.21 Variation 21: Cleavage of a Double Bond by Hydrolysis ofTetrakis(alkylsulfonyl)ethenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151

39.2.2.1.8.22 Variation 22: Pinacol Coupling by Reduction with a Vanadium(III) Reagent . 15239.2.2.1.8.23 Variation 23: Base-Catalyzed Cyclopropanation of g-Chloropropyl Sulfones 152

39.2.2.2 Applications of Product Subclass 2 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . . 152

39.2.2.2.1 Method 1: Cyclization of Bis(chloromethyl) Sulfone with Cinnamaldehyde 15239.2.2.2.2 Method 2: Alkene Synthesis by Coupling of Sulfone a,a¢-Dicarbanions . . 153

39.2.3 Product Subclass 3: S,S-Dialkylsulfoximides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154


39.2.3.1.1 Method 1: Oxidation of Sulfimides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15539.2.3.1.1.1 Variation 1: Oxidation with Potassium Permanganate . . . . . . . . . . . . . . . . . . . 15539.2.3.1.1.2 Variation 2: Oxidation with Peroxy Compounds . . . . . . . . . . . . . . . . . . . . . . . . . 15539.2.3.1.1.3 Variation 3: Oxidation with Halogen-Containing Compounds . . . . . . . . . . . . 15639.2.3.1.1.4 Variation 4: Oxidation with Dioxiranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15639.2.3.1.2 Method 2: Imination of Sulfoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15739.2.3.1.2.1 Variation 1: Reaction with Hydrazoic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15739.2.3.1.2.2 Variation 2: Reaction with Azides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15839.2.3.1.2.3 Variation 3: Reaction with Chloramine-T or Its Analogues . . . . . . . . . . . . . . . . 15939.2.3.1.2.4 Variation 4: Reaction with 2-[(Aminooxy)sulfonyl]-1,3,5-trimethylbenzene 15939.2.3.1.2.5 Variation 5: Imination with Primary Amines in the Presence of tert-Butyl

Hypochlorite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15939.2.3.1.2.6 Variation 6: Imination with Primary Amines in the Presence of Lead(IV)

Acetate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16039.2.3.1.2.7 Variation 7: Rhodium-Catalyzed Imination of Sulfoxides Using (Diacetoxy-

iodo)benzene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16039.2.3.1.2.8 Variation 8: Electrochemical Imination of Sulfoxides . . . . . . . . . . . . . . . . . . . . . 16139.2.3.1.2.9 Variation 9: Reaction of Dialkyl Sulfoxides with Quinone Monoimides . . . . 16239.2.3.1.3 Method 3: Cleavage of N-Substituent Groups . . . . . . . . . . . . . . . . . . . . . . . . . . 16239.2.3.1.3.1 Variation 1: N-Tosyl Group Cleavage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16239.2.3.1.3.2 Variation 2: N-(tert-Butoxycarbonyl) Group Cleavage . . . . . . . . . . . . . . . . . . . . 16339.2.3.1.3.3 Variation 3: Optical Resolution of S,S-Dialkylsulfoximides . . . . . . . . . . . . . . . . 16339.2.3.1.4 Method 4: Functionalization at the Nitrogen Atom . . . . . . . . . . . . . . . . . . . . . 16439.2.3.1.4.1 Variation 1: N-Arylation of Sulfoximides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16439.2.3.1.4.2 Variation 2: N-Acylation and Related Reactions . . . . . . . . . . . . . . . . . . . . . . . . . 16539.2.3.1.4.3 Variation 3: Functionalization with Heteroatom-Containing Reagents . . . . 166


39.2.3.2.1 Method 1: Reactions of a-Anions of S,S-Dialkyl-N-tosylsulfoximides . . . . . 16739.2.3.2.1.1 Variation 1: Addition to Carbonyl Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16739.2.3.2.1.2 Variation 2: Addition to Enones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16739.2.3.2.1.3 Variation 3: Addition to Imines To Form b-Aminosulfoximides . . . . . . . . . . . 16939.2.3.2.1.4 Variation 4: Intramolecular Cyclization in the Preparation of

1-Methyl-1,2-thiazine 1-Oxide Derivatives . . . . . . . . . . . . . . . . . . . 17039.2.3.2.1.5 Variation 5: Synthesis of Diazenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172

39.2.4 Product Subclass 4: S,S-Dialkyl Sulfonediimines . . . . . . . . . . . . . . . . . . . . . . . . . . 173


Table of Contents XIX


39.2.4.1.1 Method 1: Bisimination of Sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17339.2.4.1.2 Method 2: Imination of Sulfimides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17339.2.4.1.3 Method 3: Functionalization of the Nitrogen Atoms . . . . . . . . . . . . . . . . . . . . 17439.2.4.1.3.1 Variation 1: N-Acylation of Sulfonediimines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17439.2.4.1.3.2 Variation 2: N-Arylation and Related Reactions of Sulfonediimines . . . . . . . 174


39.2.4.2.1 Method 1: Synthesis of Aromatic Nitriles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17539.2.4.2.2 Method 2: Synthesis of 1l6d2,2,6-thiadiazines . . . . . . . . . . . . . . . . . . . . . . . . . 17639.2.4.2.2.1 Variation 1: Reaction of S-Alkyl-S-benzyl Sulfonediimines with Activated

Carbonyl Substrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17639.2.4.2.2.2 Variation 2: Reaction of S,S-Dialkyl Sulfonediimines with Ketene

Dithioacetals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17739.2.4.2.3 Method 3: Synthesis of 1l6,2,4-Thiadiazines . . . . . . . . . . . . . . . . . . . . . . . . . . . 17839.2.4.2.4 Method 4: Synthesis of 1l4,2,4,6-Thiatriazines . . . . . . . . . . . . . . . . . . . . . . . . . 17839.2.4.2.4.1 Variation 1: Reaction of S-Alkyl-S-benzyl Sulfonediimines with

N-Cyanoimidates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17939.2.4.2.4.2 Variation 2: Reaction of S,S-Dimethyl Sulfonediimines with

Cyanimidocarbonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17939.2.4.2.5 Method 5: Synthesis of 1l6d2,2,5-Thiadiazoles . . . . . . . . . . . . . . . . . . . . . . . . . 180

39.3 Product Class 3: Alkanesulfinic Acids and Acyclic DerivativesS. Braverman, M. Cherkinsky, and S. Levinger

39.3 Product Class 3: Alkanesulfinic Acids and Acyclic Derivatives . . . . . . . . . . . . . 187

39.3.1 Product Subclass 1: Alkylsulfur Trihalides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187


39.3.1.1.1 Method 1: Synthesis of Methylsulfur Trifluoride . . . . . . . . . . . . . . . . . . . . . . . . 18739.3.1.1.2 Method 2: Synthesis of Alkylsulfur Trichlorides . . . . . . . . . . . . . . . . . . . . . . . . . 18839.3.1.1.2.1 Variation 1: Reaction of Symmetrical Disulfides with Chlorine . . . . . . . . . . . . 18839.3.1.1.2.2 Variation 2: Reaction of Thiols with Chlorine . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188

39.3.2 Product Subclass 2: Alkanesulfinyl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188


39.3.2.1.1 Method 1: Direct Functionalization of Adamantane . . . . . . . . . . . . . . . . . . . . 18939.3.2.1.2 Method 2: Synthesis from Thiols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18939.3.2.1.2.1 Variation 1: Using Sulfuryl Chloride and Acetic Acid . . . . . . . . . . . . . . . . . . . . . 19039.3.2.1.2.2 Variation 2: Using Sulfuryl Chloride and Trimethylsilyl Acetate . . . . . . . . . . . 19039.3.2.1.3 Method 3: Synthesis from Sulfinic Acids or Sulfinate Salts . . . . . . . . . . . . . . 19139.3.2.1.3.1 Variation 1: Via a Sulfinate Generated In Situ from a Grignard Compound 19139.3.2.1.4 Method 4: Synthesis from Symmetrical Disulfides . . . . . . . . . . . . . . . . . . . . . . 19239.3.2.1.5 Method 5: Synthesis from Sulfenyl Compounds . . . . . . . . . . . . . . . . . . . . . . . . 19439.3.2.1.5.1 Variation 1: Halogenolysis of Thiosulfinate Esters . . . . . . . . . . . . . . . . . . . . . . . 19439.3.2.1.5.2 Variation 2: Oxidative Halogenolysis of S-Alkyl Thioacetates . . . . . . . . . . . . . 19439.3.2.1.5.3 Variation 3: Oxidation of Alkanesulfenyl Chlorides . . . . . . . . . . . . . . . . . . . . . . . 19539.3.2.1.6 Method 6: Synthesis from 2-(Trimethylsilyl)ethyl Sulfoxides . . . . . . . . . . . . 196

XX Table of Contents


39.3.3 Product Subclass 3: Alkanesulfinic Acids and Salts . . . . . . . . . . . . . . . . . . . . . . . 196


39.3.3.1.1 Method 1: Oxidation of Alkanethiols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19739.3.3.1.2 Method 2: Hydrolysis of Alkanesulfinyl Chlorides and Alkanesulfinic Acid

Esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19839.3.3.1.3 Method 3: Oxidative Cleavage of Dialkyl Disulfides . . . . . . . . . . . . . . . . . . . . . 19939.3.3.1.4 Method 4: Hydrolysis of Sulfinamides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20039.3.3.1.5 Method 5: Reduction of Alkanesulfonyl Halides . . . . . . . . . . . . . . . . . . . . . . . . 20039.3.3.1.5.1 Variation 1: From Alkanesulfonyl Chlorides by Reduction with Alkali Metal

Sulfites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20139.3.3.1.5.2 Variation 2: From Alkanesulfonyl Chlorides by Reduction with

4-Toluenethiol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20139.3.3.1.5.3 Variation 3: Additional Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20239.3.3.1.6 Method 6: Reductive Cleavage of Alkanethiosulfonates . . . . . . . . . . . . . . . . 20339.3.3.1.6.1 Variation 1: Cleavage of Acyclic Alkanethiosulfonates . . . . . . . . . . . . . . . . . . . 20339.3.3.1.6.2 Variation 2: Cleavage of Cyclic Alkanethiosulfonates . . . . . . . . . . . . . . . . . . . . 20439.3.3.1.7 Method 7: Reductive Cleavage of Sulfones . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20439.3.3.1.8 Method 8: Base-Induced Cleavage of Activated Sulfones . . . . . . . . . . . . . . . 20539.3.3.1.9 Method 9: Ring Opening of Thiirane 1,1-Dioxides and Other Cyclic

Sulfones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20839.3.3.1.10 Method 10: Insertion of Sulfur Dioxide into the Carbon—Metal Bond

of Organometallic Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20939.3.3.1.10.1 Variation 1: Reaction with Organolithium and Grignard Reagents . . . . . . . . 20939.3.3.1.10.2 Variation 2: Reaction with Organoaluminum Reagents . . . . . . . . . . . . . . . . . . 21039.3.3.1.11 Method 11: Addition of Sulfur Dioxide to Alkenes . . . . . . . . . . . . . . . . . . . . . . . 21039.3.3.1.12 Method 12: Synthesis with Retention of the Sulfinate Group

(Salt-to-Acid Transformation) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211

39.3.4 Product Subclass 4: Alkanesulfinic Acid Esters . . . . . . . . . . . . . . . . . . . . . . . . . . . 211


39.3.4.1.1 Method 1: Esterification of Sulfinic Acids and Sulfinate Anions . . . . . . . . . . 21239.3.4.1.1.1 Variation 1: Using Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21239.3.4.1.1.2 Variation 2: Using Hard Alkylating Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21239.3.4.1.2 Method 2: Nucleophilic Substitution of Sulfinyl Chlorides . . . . . . . . . . . . . . . 21339.3.4.1.2.1 Variation 1: Reaction of Alkanesulfinyl Chlorides with Alcohols . . . . . . . . . . . 21339.3.4.1.2.2 Variation 2: Reaction of Alkanesulfinyl Chlorides with

Alkoxytrimethylsilanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21539.3.4.1.3 Method 3: Oxidation of Alkanesulfenyl Chlorides and Alkanethiols . . . . . . 21639.3.4.1.4 Method 4: Oxidative Alkylation of Dialkyl Disulfides . . . . . . . . . . . . . . . . . . . . 21739.3.4.1.4.1 Variation 1: Oxidation of Disulfides with N-Bromosuccinimide . . . . . . . . . . . 21739.3.4.1.4.2 Variation 2: Via In Situ Formation of Alkanesulfinyl Chlorides from Dialkyl

Disulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21839.3.4.1.5 Method 5: Oxidation of Alkanesulfenic Acid Esters . . . . . . . . . . . . . . . . . . . . . 21939.3.4.1.6 Method 6: Cleavage of Dialkyl Sulfoxylates . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22039.3.4.1.7 Method 7: Cleavage of the S—N Bond of Alkenesulfinamides . . . . . . . . . . . 22239.3.4.1.8 Method 8: Reductive Esterification of Alkanesulfonyl Chlorides and

Other Alkanesulfonic Acid Derivatives . . . . . . . . . . . . . . . . . . . . . . 223

Table of Contents XXI


39.3.4.1.9 Method 9: Cleavage of the S—S Bond of Alkanethiosulfonates and AlkylAlkylsulfinyl Sulfones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225

39.3.4.1.10 Method 10: Substitution of Dialkyl Sulfites and Chlorosulfite Esters . . . . . . 22539.3.4.1.11 Method 11: Synthesis with Retention of the Sulfinate Group

(Transesterification) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226

39.3.5 Product Subclass 5: Alkanesulfinic Anhydrides . . . . . . . . . . . . . . . . . . . . . . . . . . . 227


39.3.5.1.1 Method 1: Synthesis from Alkanesulfinyl Chlorides and Silver Sulfinates . 227

39.3.6 Product Subclass 6: Alkylthiosulfinato Transition-Metal Complexes . . . . . . 227


39.3.6.1.1 Method 1: Synthesis by Substitution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22739.3.6.1.2 Method 2: Synthesis by Oxidative Addition . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228

39.3.7 Product Subclass 7: Alkanethiosulfinic Acid Esters . . . . . . . . . . . . . . . . . . . . . . . 229


39.3.7.1.1 Method 1: Synthesis from Alkanesulfinyl Chlorides . . . . . . . . . . . . . . . . . . . . . 22939.3.7.1.1.1 Variation 1: By Reaction with Thiols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22939.3.7.1.1.2 Variation 2: By Reaction with Organotin Thiolates . . . . . . . . . . . . . . . . . . . . . . . 23039.3.7.1.2 Method 2: Synthesis from Dialkyl Disulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . 23039.3.7.1.2.1 Variation 1: By Oxidation with Hydrogen Peroxide . . . . . . . . . . . . . . . . . . . . . . . 23139.3.7.1.2.2 Variation 2: By Oxidation with Perbenzoic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . 23139.3.7.1.2.3 Variation 3: By Oxidation with 3-Chloroperoxybenzoic Acid . . . . . . . . . . . . . . 23239.3.7.1.2.4 Variation 4: By Oxidation with Dimethyldioxirane . . . . . . . . . . . . . . . . . . . . . . . 23239.3.7.1.2.5 Variation 5: By Photooxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23339.3.7.1.2.6 Variation 6: By Asymmetric Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233

39.3.8 Product Subclass 8: Alkanesulfinamides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235


39.3.8.1.1 Method 1: Synthesis from Alkanesulfinyl Chlorides . . . . . . . . . . . . . . . . . . . . . 23539.3.8.1.2 Method 2: Synthesis from Alkanesulfinic Acids . . . . . . . . . . . . . . . . . . . . . . . . . 23639.3.8.1.3 Method 3: Synthesis from Alkanesulfinate or Alkanethiosulfinate Esters . 23639.3.8.1.3.1 Variation 1: Chiral Alkanesulfinamides Using an Amino Alcohol and

Thionyl Chloride via Alkanesulfinate Esters . . . . . . . . . . . . . . . . . . 23739.3.8.1.3.2 Variation 2: Alkanesulfinamides from Alkanethiosulfinate Esters . . . . . . . . . 238

39.4 Product Class 4: Acyclic Dialkyl Sulfoxides and DerivativesJ. L. Garc4a Ruano, M. B. Cid, A. M. Mart4n-Castro, and J. Alem8n

39.4 Product Class 4: Acyclic Dialkyl Sulfoxides and Derivatives . . . . . . . . . . . . . . . 245

39.4.1 Product Subclass 1: Acyclic Diheterosubstituted Dialkyl-l4-sulfanes . . . . . 246


39.4.2 Product Subclass 2: Acyclic Dialkyl Sulfoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249


39.4.2.1.1 Optically Inactive Dialkyl Sulfoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250

XXII Table of Contents


39.4.2.1.1.1 Method 1: Synthesis from Alkanesulfenic Acid Derivatives . . . . . . . . . . . . . . 25039.4.2.1.1.1.1 Variation 1: Addition of Sulfenic Acids to Alkenes . . . . . . . . . . . . . . . . . . . . . . . 25039.4.2.1.1.1.2 Variation 2: Rearrangement of Sulfenic Acid Esters . . . . . . . . . . . . . . . . . . . . . . 25039.4.2.1.1.1.3 Variation 3: Electrophilic Addition to Sulfenic Acid Salts . . . . . . . . . . . . . . . . . 25139.4.2.1.1.2 Method 2: Synthesis from Sulfinyl Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . 25239.4.2.1.1.2.1 Variation 1: From Thionyl Chloride or Related Compounds . . . . . . . . . . . . . . . 25239.4.2.1.1.2.2 Variation 2: From Alkanesulfinic Acid Derivatives . . . . . . . . . . . . . . . . . . . . . . . . 25339.4.2.1.1.3 Method 3: Oxidation of Dialkyl Sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25439.4.2.1.1.3.1 Variation 1: Using Oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25439.4.2.1.1.3.2 Variation 2: Using Hydrogen Peroxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26039.4.2.1.1.3.3 Variation 3: Using Peroxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26739.4.2.1.1.3.4 Variation 4: Using Peroxy Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26939.4.2.1.1.3.5 Variation 5: Using Halogen Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27139.4.2.1.1.3.6 Variation 6: Using Nitrogen Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28539.4.2.1.1.3.7 Variation 7: Using Other Oxidizing Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28939.4.2.1.1.4 Method 4: Synthesis from Other Sulfur Derivatives . . . . . . . . . . . . . . . . . . . . . 29939.4.2.1.1.4.1 Variation 1: From Sulfonium Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29939.4.2.1.1.4.2 Variation 2: From Sulfimides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29939.4.2.1.1.4.3 Variation 3: From Organosulfur(VI) Compounds . . . . . . . . . . . . . . . . . . . . . . . . . 29939.4.2.1.1.4.4 Variation 4: From Sulfoxonium Ylides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30039.4.2.1.1.4.5 Variation 5: From Thioketone S-Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300

39.4.2.1.2 Optically Active Dialkyl Sulfoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301

39.4.2.1.2.1 Method 1: Synthesis from Sulfinyl Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . 30139.4.2.1.2.1.1 Variation 1: From Alkanesulfinic Acid Esters and Sulfites: Oxygen

Functions as the Leaving Group . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30139.4.2.1.2.1.2 Variation 2: From Alkanesulfinamides and Sulfites: Nitrogen Functions

as the Leaving Group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30939.4.2.1.2.1.3 Variation 3: From Optically Pure Sulfoxides: Carbon Functions as the

Leaving Group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31439.4.2.1.2.1.4 Variation 4: From Thiosulfinates by EllmanQs Thiosulfinate Synthesis:

Sulfur Functions as the Leaving Group . . . . . . . . . . . . . . . . . . . . . . 32039.4.2.1.2.2 Method 2: Oxidation of Dialkyl Sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32139.4.2.1.2.2.1 Variation 1: Using Achiral Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32139.4.2.1.2.2.2 Variation 2: Using Alkyl Peroxides and Chiral Metal Catalysts . . . . . . . . . . . . . 32239.4.2.1.2.2.3 Variation 3: Using Other Chiral Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32639.4.2.1.2.2.4 Variation 4: Biological Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33039.4.2.1.2.3 Method 3: Resolution of Racemic Mixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33539.4.2.1.2.3.1 Variation 1: Spontaneous Resolution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33539.4.2.1.2.3.2 Variation 2: Kinetic Resolution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 336


39.4.2.2.1 Method 1: Oxidation of Alcohols by Dimethyl Sulfoxide andDicyclohexylcarbodiimide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 338

39.4.2.2.2 Method 2: Oxidation of Alcohols by Dimethyl Sulfoxide and OxalylChloride (Swern Oxidation) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 341

39.4.2.2.3 Method 3: Oxidation by Dimethyl Sulfoxide in the Presence of OtherActivating Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 346

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39.4.2.2.4 Method 4: Oxidation of Organic Halides and Sulfonates with DimethylSulfoxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348

39.4.2.2.5 Method 5: The Halogen–Dimethyl Sulfoxide System as an OxidizingReagent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 349

39.4.2.2.6 Method 6: Oxidation of Other Functional Groups by Dimethyl Sulfoxide . 35139.4.2.2.7 Method 7: Epoxide Ring-Opening Reactions by Dimethyl Sulfoxide . . . . . . 352

39.4.3 Product Subclass 3: Acyclic S,S-Dialkylsulfimides . . . . . . . . . . . . . . . . . . . . . . . . . 352


39.4.3.1.1 Optically Inactive S,S-Dialkylsulfimides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353

39.4.3.1.1.1 Method 1: Oxidative Amination of Sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35339.4.3.1.1.1.1 Variation 1: Reaction with N-Halo Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . 35339.4.3.1.1.1.2 Variation 2: Reaction with Azides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35939.4.3.1.1.1.3 Variation 3: Reaction with Other Sources of Electrophilic Nitrogen . . . . . . . 36139.4.3.1.1.2 Method 2: Amination of Sulfoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36239.4.3.1.1.2.1 Variation 1: Reaction with Compounds Containing an Amino Group . . . . . . 36239.4.3.1.1.2.2 Variation 2: Reaction with Heterocumulenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36539.4.3.1.1.3 Method 3: Synthesis of N-Unsubstituted S,S-Dialkylsulfimides . . . . . . . . . . 365

39.4.3.1.2 Optically Active S,S-Dialkylsulfimides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 366


39.4.3.2.1 Method 1: Synthesis of Sulfur Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36739.4.3.2.1.1 Variation 1: Reduction To Form Sulfides and Amines . . . . . . . . . . . . . . . . . . . . 36739.4.3.2.1.2 Variation 2: Synthesis of Sulfoximides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36939.4.3.2.1.3 Variation 3: Synthesis of Other Organosulfur Compounds . . . . . . . . . . . . . . . 36939.4.3.2.2 Method 2: Synthesis of Heterocycles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37039.4.3.2.2.1 Variation 1: Transformation via Nitrene Intermediates by Photolysis and

Thermolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37039.4.3.2.2.2 Variation 2: Reactions of Sulfimides with Electrophiles . . . . . . . . . . . . . . . . . . 37139.4.3.2.2.3 Variation 3: Methylation of Heterocycles via S,S-Dialkylsulfimides . . . . . . . . 37439.4.3.2.2.4 Variation 4: Conversion of Amines into Nitroso and Nitro Compounds . . . . 374

39.5 Product Class 5: AlkanethiolsJ. V. Comasseto and A. S. Guarezemini

39.5 Product Class 5: Alkanethiols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391

39.5.1 Synthesis of Product Class 5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391

39.5.1.1 Method 1: Insertion of Elemental Sulfur into an Alkyllithium or AlkylGrignard Reagent Followed by Reaction with an Acid . . . . . . . . 391

39.5.1.2 Method 2: Reaction of an Alkylating Agent with a Nucleophilic SulfurSpecies Followed by Hydrolysis or Reduction . . . . . . . . . . . . . . . . 391

39.5.1.2.1 Variation 1: Reaction of Alkylating Agents with Hydrosulfides or SodiumThiosulfate Followed by Acidic Hydrolysis . . . . . . . . . . . . . . . . . . . 392

39.5.1.2.2 Variation 2: Transformation of Alcohols into Alkanethiols . . . . . . . . . . . . . . . . 39439.5.1.2.3 Variation 3: Thiols from Dithiocarbonates, Thioacetates, or Related

Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39539.5.1.2.4 Variation 4: Alkanethiols from Thiouronium Salts or Related Compounds . 398

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39.5.1.3 Method 3: Reduction of Alkanesulfonyl Chlorides . . . . . . . . . . . . . . . . . . . . . . 39939.5.1.4 Method 4: Alkanethiols from Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39939.5.1.4.1 Variation 1: Reaction of Alkenes with Hydrogen Sulfide . . . . . . . . . . . . . . . . . . 39939.5.1.4.2 Variation 2: Reaction of Alkenes with Thioacetic Acid or Thiols Followed

by Transformation of the Products into Alkanethiols . . . . . . . . . 40039.5.1.4.3 Variation 3: Reaction of Thiocarbonyl Compounds with Alkenes Followed

by Cleavage of the Adduct . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40039.5.1.5 Method 5: Reduction of Thiocyanates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40139.5.1.6 Method 6: Reduction of Disulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40139.5.1.6.1 Variation 1: By Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40239.5.1.6.2 Variation 2: By Complex Metal Hydrides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40239.5.1.6.3 Variation 3: By Trisubstituted Phosphines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40339.5.1.7 Method 7: C—S Bond Cleavage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40339.5.1.7.1 Variation 1: Aminolysis of Thiiranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40339.5.1.7.2 Variation 2: Reductive Cleavage of C—S Bonds . . . . . . . . . . . . . . . . . . . . . . . . . . 40439.5.1.8 Method 8: Alkanethiols from Heterocyclic Compounds . . . . . . . . . . . . . . . . . 405

39.6 Product Class 6: Acyclic Alkanethiolates

39.6.1 Product Subclass 1: Alkanethiolates of Group 1, 2, and 13–15 MetalsJ. V. Comasseto and A. S. Guarezemini

39.6.1 Product Subclass 1: Alkanethiolates of Group 1, 2, and 13–15 Metals . . . . 413


39.6.1.1.1 Arsenic Alkanethiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 413

39.6.1.1.1.1 Method 1: Reaction of Arsenic Halides with Alkanethiols orAlkanethiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 413

39.6.1.1.1.2 Method 2: Reaction of Arsenoxides with Alkanethiols . . . . . . . . . . . . . . . . . . 41439.6.1.1.1.3 Method 3: Reaction of Aminoarsines with Alkanethiols . . . . . . . . . . . . . . . . . 41439.6.1.1.1.4 Method 4: Reaction of Tetraalkyldiarsines with Dialkyl Disulfides . . . . . . . . 41539.6.1.1.1.5 Method 5: Reaction of Arsenic(III) Fluoride with (tert-Butylsulfanyl)tri-

methylsilane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 415

39.6.1.1.2 Antimony Alkanethiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 415

39.6.1.1.2.1 Method 1: Reaction of Antimony(III) Chloride with Alkanethiols orAlkanethiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 416

39.6.1.1.2.2 Method 2: Reaction of Antimony(III) Fluoride with (tert-Butylsulfanyl)tri-methylsilane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 416

39.6.1.1.2.3 Method 3: Transmetalation Reactions of Zirconocene Metallocycles andAntimony Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 416

39.6.1.1.3 Bismuth Alkanethiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 417

39.6.1.1.3.1 Method 1: Reaction of Bismuth Halides, Alkoxides, and Nitrates withAlkanethiols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 417

39.6.1.1.3.2 Method 2: Reaction of Bismuth(III) Fluoride with (tert-Butylsulfanyl)tri-methylsilane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 417

39.6.1.1.4 Silicon Alkanethiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 418

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39.6.1.1.4.1 Method 1: Reaction of Chlorosilanes with Alkanethiols or Alkanethiolates 41839.6.1.1.4.2 Method 2: Alkylation of Lithium Silicon Thiolates . . . . . . . . . . . . . . . . . . . . . . . 41939.6.1.1.4.3 Method 3: Cleavage of S—C Bonds of Alkyl Sulfides . . . . . . . . . . . . . . . . . . . . 41939.6.1.1.4.3.1 Variation 1: Radical Reaction of Thioacetals with Tris(trimethylsilyl)silane . 41939.6.1.1.4.3.2 Variation 2: Acid-Catalyzed Thiirane Opening with Trimethylsilyl Cyanide . 41939.6.1.1.4.4 Method 4: Reaction of a Thiocarbonyl Compound with a Silylene . . . . . . . 420

39.6.1.1.5 Germanium Alkanethiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 420

39.6.1.1.5.1 Method 1: Reaction of Germyl Halides and Oxides with Alkanethiolates . 42039.6.1.1.5.2 Method 2: Reaction of Halogermanes with Tetrakis(methanethio-

lato)aluminate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 421

39.6.1.1.6 Tin Alkanethiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 421

39.6.1.1.6.1 Method 1: Reaction of Organotin Halides with Alkanethiols in thePresence of a Base . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 421

39.6.1.1.6.2 Method 2: Thiolysis of Alkyltin Alkoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 422

39.6.1.1.7 Lead Alkanethiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 422

39.6.1.1.7.1 Method 1: Reaction of Triorganolead Chlorides or Hydroxides withAlkanethiols or Lead(II) Thiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . 422

39.6.1.1.7.2 Method 2: Disproportionation of Diplumbanes with Dialkyl Disulfides . . . 423

39.6.1.1.8 Boron Alkanethiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 423

39.6.1.1.8.1 Method 1: Reaction of Boranes with Alkanethiols . . . . . . . . . . . . . . . . . . . . . . 42339.6.1.1.8.2 Method 2: Reaction of Haloboranes with Alkanethiols or Alkali Metal

Thiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 424

39.6.1.1.9 Aluminum Alkanethiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 424

39.6.1.1.9.1 Method 1: Reaction of Trialkylaluminums with Alkanethiols . . . . . . . . . . . . 42439.6.1.1.9.2 Method 2: Reaction of Aluminum Halides and Amides with Alkanethiols

or Sodium Alkanethiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42539.6.1.1.9.3 Method 3: Reaction of Piperidinylaluminum Halides with Lithium

Alkanethiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42539.6.1.1.9.4 Method 4: Reaction of Aluminum Hydrides with Alkanethiols . . . . . . . . . . . 426

39.6.1.1.10 Gallium Alkanethiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 427

39.6.1.1.10.1 Method 1: Reaction of Gallium Halides with Metal Thiolates . . . . . . . . . . . . 42739.6.1.1.10.2 Method 2: Reaction of Triorganogallium Species with Alkanethiols . . . . . . 427

39.6.1.1.11 Indium Alkanethiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 428

39.6.1.1.11.1 Method 1: Reaction of Organoindium Compounds with Alkanethiols . . . . 42839.6.1.1.11.2 Method 2: Reaction of Indium(III) tert-Butyl(trimethylsilyl)amide with

Alkanethiols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 428

39.6.1.1.12 Thallium Alkanethiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 428

39.6.1.1.12.1 Method 1: Reaction of Thallium Salts with Alkanethiols or SodiumAlkanethiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 429

39.6.1.1.13 Beryllium Alkanethiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 429

39.6.1.1.14 Magnesium Alkanethiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 429

39.6.1.1.15 Calcium Alkanethiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 430

XXVI Table of Contents


39.6.1.1.16 Strontium Alkanethiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 430

39.6.1.1.17 Barium Alkanethiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 430

39.6.1.1.18 Lithium Alkanethiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 431

39.6.1.1.18.1 Method 1: Reaction of Alkanethiols with Butyllithium . . . . . . . . . . . . . . . . . . 43139.6.1.1.18.2 Method 2: Reaction of Elemental Sulfur with Alkyllithium Compounds . . 431

39.6.1.1.19 Sodium Alkanethiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 431

39.6.1.1.19.1 Method 1: Reaction of Alkanethiols with a Base . . . . . . . . . . . . . . . . . . . . . . . . 43139.6.1.1.19.2 Method 2: Reaction of Alkanethiols with Sodium . . . . . . . . . . . . . . . . . . . . . . 43239.6.1.1.19.3 Method 3: Reaction of Dialkyl Disulfides with Sodium . . . . . . . . . . . . . . . . . . 432

39.6.2 Product Subclass 2: Alkanethiolates of Group 3–12 MetalsA. Polo and J. Real

39.6.2 Product Subclass 2: Alkanethiolates of Group 3–12 Metals . . . . . . . . . . . . . . . 437


39.6.2.1.1 Terminal Alkanethiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 437

39.6.2.1.1.1 Method 1: Reaction of Metal Halides with Alkanethiols or Main GroupAlkanethiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 437

39.6.2.1.1.1.1 Variation 1: Reaction of a Metal Chloro Complex with an Alkanethiol . . . . . 43739.6.2.1.1.1.2 Variation 2: Reactions of a Metal Complex with an Alkanethiol in the

Presence of a Base . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43839.6.2.1.1.1.3 Variation 3: Reaction of a Metal Complex with a Main Group

Alkanethiolate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44039.6.2.1.1.1.4 Variation 4: Reaction of a Metal Complex with an Alkanethiol and a

Reducing Agent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44439.6.2.1.1.2 Method 2: Reaction of an Alkanethiol with a Basic Ligand Complex with

Displacement of the Protonated Ligand . . . . . . . . . . . . . . . . . . . . . 44439.6.2.1.1.3 Method 3: Reaction of Coordinated Sulfides with Electrophiles . . . . . . . . . 44639.6.2.1.1.4 Method 4: Oxidative Addition of a Dialkyl Disulfide to a Metal Center . . . 44739.6.2.1.1.5 Methods 5: Miscellaneous Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 449

39.6.2.1.2 Homometallic m-Alkanethiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 450

39.6.2.1.2.1 Method 1: Reaction of a Metal Complex with an Alkanethiol or with aMain Group Alkanethiolate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 450

39.6.2.1.2.1.1 Variation 1: Reaction of a Metal Complex with an Alkanethiol . . . . . . . . . . . . 45039.6.2.1.2.1.2 Variation 2: Reaction of a Metal Complex with an Alkanethiol and a Base . 45139.6.2.1.2.1.3 Variation 3: Reaction of a Metal Complex with a Main Group Alkanethio-

late . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45239.6.2.1.2.2 Method 2: Reaction of an Alkanethiol with a Basic Ligand Complex

with Displacement of the Protonated Ligand . . . . . . . . . . . . . . . . 45339.6.2.1.2.3 Method 3: Reaction of Bridging Coordinated Sulfides with Electrophiles . 45339.6.2.1.2.4 Method 4: Oxidative Addition of an Alkanethiol or a Dialkyl Disulfide

to a Metal Complex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45439.6.2.1.2.4.1 Variation 1: By Oxidative Addition of an Alkanethiol to a Metal Complex . 45439.6.2.1.2.4.2 Variation 2: Oxidative Addition of a Dialkyl Disulfide to a Metal Complex . 455

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39.6.2.1.2.4.3 Variation 3: Photochemically Assisted Oxidative Addition of an AlkylDisulfide to a Metal Complex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 455

39.6.2.1.2.5 Method 5: Synthesis of Bridging Alkanethiolates by Ligand Dissociation . 45639.6.2.1.2.6 Method 6: Reaction of an Alkanethiolate–Metal Complex with a Second

Metal Complex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45739.6.2.1.2.7 Methods 7: Miscellaneous Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 457

39.6.2.1.3 Heterometallic m-Alkanethiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 458

39.6.2.1.3.1 Method 1: Reaction of Bridging Coordinated Sulfides with Electrophiles . 45839.6.2.1.3.2 Method 2: Reaction of an Alkanethiolate–Metal Complex with a Second

Metal Complex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 459

39.6.2.1.4 m3-Alkanethiolates and Higher Bridging mn-Alkanethiolates . . . . . . . . . . . . . . . . . . 459

39.6.2.1.4.1 Method 1: Reaction of a Metal Complex with an Alkanethiol, a DialkylDisulfide, or a Main Group Alkanethiolate . . . . . . . . . . . . . . . . . . . 460

39.6.2.1.4.2 Method 2: Reaction of Bridging Coordinated Sulfides with Electrophiles . 460


39.6.2.2.1 Method 1: Metal-Catalyzed C—S Bond Formation Reactions . . . . . . . . . . . . 46239.6.2.2.2 Method 2: Catalytic Propargylic Substitution Reactions . . . . . . . . . . . . . . . . . 46239.6.2.2.3 Method 3: Catalytic Carbonylation Reactions with Alkanethiolate

Catalyst Precursors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46339.6.2.2.4 Method 4: Stereoselective [3 + 2] Dipolar Cycloaddition of Nitrones to

Electron-Deficient Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 463

39.7 Product Class 7: Acyclic Dialkyl SulfidesS. Fujiwara and M. Toyofuku

39.7 Product Class 7: Acyclic Dialkyl Sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 469

39.7.1 Synthesis of Product Class 7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 469

39.7.1.1 Method 1: Synthesis from Alkanethiols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46939.7.1.1.1 Variation 1: By Substitution of Alkyl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46939.7.1.1.2 Variation 2: By Substitution of Sulfonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47039.7.1.1.3 Variation 3: By Substitution of Alcohols and Carbonates . . . . . . . . . . . . . . . . . 47139.7.1.1.4 Variation 4: By Ring Opening of Cyclic Ethers . . . . . . . . . . . . . . . . . . . . . . . . . . . 47239.7.1.1.5 Variation 5: By Addition to Simple Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47439.7.1.1.6 Variation 6: By Addition to Electron-Deficient Alkenes . . . . . . . . . . . . . . . . . . . 47539.7.1.2 Method 2: Synthesis from Alkanethiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47739.7.1.2.1 Variation 1: By Substitution of Alkyl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47839.7.1.2.2 Variation 2: By Substitution of Alkyl Sulfonates . . . . . . . . . . . . . . . . . . . . . . . . . . 47939.7.1.2.3 Variation 3: By Substitution with Alkyl Carbonates . . . . . . . . . . . . . . . . . . . . . . 48039.7.1.2.4 Variation 4: By Substitution of Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48139.7.1.2.5 Variation 5: By Substitution of Cyclic Ethers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48139.7.1.3 Method 3: Synthesis from Disulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48139.7.1.3.1 Variation 1: By Metal–Sulfur Exchange with Alkyl Metals . . . . . . . . . . . . . . . . . 48139.7.1.3.2 Variation 2: By Reaction with Alkyl Halides or 4-Toluenesulfonates via

Thiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48239.7.1.3.3 Variation 3: By Addition to Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 483

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39.7.1.3.4 Variation 4: By Desulfurization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48439.7.1.4 Method 4: Synthesis from Thioacetal Derivatives . . . . . . . . . . . . . . . . . . . . . . 48439.7.1.4.1 Variation 1: By C—S Bond Cleavage of Dithioacetals . . . . . . . . . . . . . . . . . . . . . 48439.7.1.4.2 Variation 2: By C—O Bond Cleavage of Siloxy Monothioacetals . . . . . . . . . . . 48639.7.1.5 Method 5: Synthesis from Thioesters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48639.7.1.6 Method 6: Synthesis from Sulfonium Ylides . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48639.7.1.7 Method 7: Synthesis from Acyclic Sulfoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . 48739.7.1.7.1 Variation 1: By Reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48739.7.1.7.2 Variation 2: By Sulfanylation of Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48839.7.1.8 Method 8: Synthesis from Acyclic Sulfones . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48839.7.1.9 Methods 9: Miscellaneous Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 488

39.7.2 Applications of Product Class 7 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . . . . . 489

39.7.2.1 Method 1: Use as Reducing Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48939.7.2.1.1 Variation 1: Reduction of Sulfoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48939.7.2.1.2 Variation 2: Reduction of Ozonides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49039.7.2.2 Method 2: Use as Oxidizing Agents for Alcohols . . . . . . . . . . . . . . . . . . . . . . . 49139.7.2.3 Method 3: Use as Dealkylating Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49339.7.2.4 Method 4: Use as Protecting Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49439.7.2.5 Method 5: Use as Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49539.7.2.6 Method 6: Use as Ligands for Transiton-Metal Catalysts . . . . . . . . . . . . . . . . 496

39.8 Product Class 8: Acyclic Trialkyloxosulfonium and TrialkylsulfoniumSalts and DerivativesY. Tang and X.-L. Sun

39.8 Product Class 8: Acyclic Trialkyloxosulfonium and TrialkylsulfoniumSalts and Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 501

39.8.1 Product Subclass 1: Acyclic Trialkyloxosulfonium Salts . . . . . . . . . . . . . . . . . . . 501


39.8.1.1.1 Method 1: Reaction of Sulfoxides with Alkylating Agents . . . . . . . . . . . . . . . 50139.8.1.1.2 Method 2: Reaction of Oxosulfonium Ylides . . . . . . . . . . . . . . . . . . . . . . . . . . . 50239.8.1.1.2.1 Variation 1: With Brønsted Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50239.8.1.1.2.2 Variations 2: Miscellaneous Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50339.8.1.1.3 Method 3: Oxidation of Sulfonium Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50339.8.1.1.4 Method 4: Anion Exchange of Oxosulfonium Salts . . . . . . . . . . . . . . . . . . . . . . 504

39.8.2 Product Subclass 2: Acyclic Trialkylsulfonium Salts . . . . . . . . . . . . . . . . . . . . . . . 505


39.8.2.1.1 Method 1: Reaction of Dialkyl Sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50539.8.2.1.1.1 Variation 1: With Alkylating Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50539.8.2.1.1.2 Variation 2: With Cyclopropane Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51539.8.2.1.1.3 Variation 3: With Heterocyclic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51639.8.2.1.1.4 Variation 4: With Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51939.8.2.1.1.5 Variation 5: With Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52239.8.2.1.1.6 Variation 6: With Ethers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52339.8.2.1.1.7 Variations 7: Miscellaneous Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 524

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39.8.2.1.2 Method 2: Reaction of Dialkylsulfonium Halides . . . . . . . . . . . . . . . . . . . . . . . 52539.8.2.1.2.1 Variation 1: With Diazo Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52539.8.2.1.2.2 Variation 2: With Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52539.8.2.1.2.3 Variation 3: With Dialkyl Sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52639.8.2.1.3 Method 3: Reaction of Sulfoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52739.8.2.1.3.1 Variation 1: With Grignard Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52739.8.2.1.3.2 Variation 2: With Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52739.8.2.1.4 Method 4: Reaction of Sulfonium Ylides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52939.8.2.1.4.1 Variation 1: With Brønsted Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52939.8.2.1.4.2 Variations 2: Miscellaneous Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53039.8.2.1.5 Method 5: Reaction of Thiols and Thiol Derivatives with Alkylating Agents 53139.8.2.1.6 Method 6: Reaction of Dialkyl Disulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53139.8.2.1.7 Method 7: Reaction of Alkanesulfenyl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . 53239.8.2.1.8 Method 8: Transformation of Sulfonium Salts . . . . . . . . . . . . . . . . . . . . . . . . . . 53339.8.2.1.8.1 Variation 1: Anion Exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53339.8.2.1.8.2 Variations 2: Miscellaneous Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53539.8.2.1.9 Method 9: Reduction of Oxosulfonium Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . 53639.8.2.1.10 Method 10: Reaction of Sulfur and Metal Sulfides . . . . . . . . . . . . . . . . . . . . . . . 536

39.9 Product Class 9: Alkanesulfenic Acids and Acyclic DerivativesJ. Drabowicz, P. Kiełbasinski, P. Łyzwa, and M. Mikołajczyk

39.9 Product Class 9: Alkanesulfenic Acids and Acyclic Derivatives . . . . . . . . . . . . 543

39.9.1 Product Subclass 1: Alkanesulfenyl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 544


39.9.1.1.1 Method 1: Halogenation of Divalent Sulfur Precursors . . . . . . . . . . . . . . . . . . 54439.9.1.1.1.1 Variation 1: Halogenation of Thiols, Thiol Salts, or Disulfides with Halogens 54539.9.1.1.1.2 Variation 2: Halogenation of Thiols or Disulfides with Other Halogenating

Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54739.9.1.1.1.3 Variation 3: Halogenation of Sulfides or Thiocarboxylate S-Esters . . . . . . . . 54739.9.1.1.2 Method 2: Reaction of Sulfur Dichloride with Alkenes or Carbon

Nucleophiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54939.9.1.1.2.1 Variation 1: Addition of Sulfur Dichloride to Alkenes . . . . . . . . . . . . . . . . . . . . . 54939.9.1.1.2.2 Variation 2: Reaction of Sulfur Dichloride with Carbonyl or Dicarbonyl

Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54939.9.1.1.3 Method 3: Halogen Exchange Reactions of Sulfenyl Chlorides . . . . . . . . . . . 55039.9.1.1.4 Method 4: Chlorination of Thiocarbonyl Compounds . . . . . . . . . . . . . . . . . . . 550

39.9.2 Product Subclass 2: Alkanesulfenic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 550


39.9.2.1.1 Method 1: Oxidation of Thiols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55039.9.2.1.2 Method 2: Elimination Reactions of Sulfinyl Derivatives . . . . . . . . . . . . . . . . . 55139.9.2.1.3 Methods 3: Miscellaneous Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 556

39.9.3 Product Subclass 3: Alkanesulfenic Acid Esters . . . . . . . . . . . . . . . . . . . . . . . . . . . 557


39.9.3.1.1 Method 1: Reaction of Sulfenyl Halides with Phenols or Alcohols . . . . . . . . 557

XXX Table of Contents


39.9.3.1.2 Method 2: Reaction of N-(Alkylsulfanyl)phthalimides with Alcoholsor Metal Alkoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 559

39.9.3.1.3 Method 3: Reaction of Thiirane 1-Oxide with Chloromethyl Ethers . . . . . . 56039.9.3.1.4 Method 4: Reaction of Sulfenyl Chlorides with Epoxides . . . . . . . . . . . . . . . . 56039.9.3.1.5 Method 5: Transesterification of Sulfenates . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56039.9.3.1.6 Methods 6: Miscellaneous Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 561

39.9.4 Product Subclass 4: Alkanesulfenamides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 561


39.9.4.1.1 Method 1: Synthesis from Sulfenyl Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . 56139.9.4.1.1.1 Variation 1: Reaction of Sulfenyl Halides with Ammonia and Amines . . . . . 56139.9.4.1.1.2 Variation 2: Reaction of Sulfenyl Thiocyanates with Amines . . . . . . . . . . . . . . 56539.9.4.1.1.3 Variation 3: Reaction of S-Alkyl Thiosulfonates with Amines . . . . . . . . . . . . . 56539.9.4.1.1.4 Variation 4: Reaction of N-(Alkylsulfanyl)phthalimides with Amines . . . . . . 56639.9.4.1.1.5 Variation 5: Reaction of 1-Alkyl-2-(alkyldisulfanyl)pyridinium Salts with

Amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56639.9.4.1.2 Method 2: Synthesis from Alkanethiols or Dialkyl Disulfides . . . . . . . . . . . . 56739.9.4.1.2.1 Variation 1: Reaction of Thiols with N-Chloroamines . . . . . . . . . . . . . . . . . . . . . 56739.9.4.1.2.2 Variation 2: Reaction of Thiols with Azides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56839.9.4.1.2.3 Variation 3: Reaction of Dialkyl Disulfides with Amines . . . . . . . . . . . . . . . . . . 56839.9.4.1.2.4 Variation 4: Reaction of Dialkyl Disulfides with Lithium Amides . . . . . . . . . . 56839.9.4.1.3 Method 3: Reaction of a Chloromethyl Sulfoxide with an Amine . . . . . . . . 56939.9.4.1.4 Method 4: Transformation of N-Alkylidene Sulfenamides . . . . . . . . . . . . . . . 569

39.10 Product Class 10: Acyclic Di- and PolysulfidesR. Sato and T. Kimura

39.10 Product Class 10: Acyclic Di- and Polysulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . 573

39.10.1 Product Subclass 1: Monoalkyl Disulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 573


39.10.1.1.1 Method 1: Preparation of Hydrodisulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57439.10.1.1.1.1 Variation 1: Preparation of Alkyl Hydrodisulfides . . . . . . . . . . . . . . . . . . . . . . . . 57439.10.1.1.1.2 Variation 2: Preparation of Haloalkyl or Hydroxyalkyl Hydrodisulfides . . . . 57439.10.1.1.2 Method 2: Preparation of Halo Disulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 574

39.10.2 Product Subclass 2: Monoalkyl Polysulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 575


39.10.2.1.1 Method 1: Preparation of Hydropolysulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . 57539.10.2.1.2 Method 2: Preparation of Chloro Polysulfides . . . . . . . . . . . . . . . . . . . . . . . . . . 575

39.10.3 Product Subclass 3: Metal Salts of Alkyl Di- and Polysulfides . . . . . . . . . . . . . 576

39.10.4 Product Subclass 4: Symmetrical Dialkyl Disulfides . . . . . . . . . . . . . . . . . . . . . . 576


39.10.4.1.1 Method 1: Oxidation of Thiols or Thiolate Ions . . . . . . . . . . . . . . . . . . . . . . . . . 57739.10.4.1.1.1 Variation 1: Oxidation with Halogens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57739.10.4.1.1.2 Variation 2: Oxidation with Peroxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57739.10.4.1.1.3 Variation 3: Oxidation with Diethyl Azodicarboxylate . . . . . . . . . . . . . . . . . . . . 578

Table of Contents XXXI


39.10.4.1.1.4 Variation 4: Metal-Ion-Catalyzed Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57839.10.4.1.1.5 Variation 5: Oxidation with Tellurite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57939.10.4.1.2 Method 2: Ring Opening and Coupling of Thiiranes . . . . . . . . . . . . . . . . . . . . 580

39.10.5 Product Subclass 5: Unsymmetrical Dialkyl Disulfides . . . . . . . . . . . . . . . . . . . . 581


39.10.5.1.1 Method 1: Thiolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58139.10.5.1.1.1 Variation 1: With Sulfenamides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58139.10.5.1.1.2 Variation 2: With Thiosulfonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58239.10.5.1.1.3 Variation 3: With Thiosulfinates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 582

39.10.6 Product Subclass 6: Symmetrical Dialkyl Polysulfides . . . . . . . . . . . . . . . . . . . . 583


39.10.6.1.1 Method 1: Reaction of Disulfides with Alkanesulfenyl Chlorides . . . . . . . . . 58339.10.6.1.1.1 Variation 1: Reaction of Thiols with Sulfur Dichloride . . . . . . . . . . . . . . . . . . . . 58339.10.6.1.1.2 Variation 2: Reaction of Thiosulfonates with Potassium Sulfide . . . . . . . . . . . 584

39.10.7 Product Subclass 7: Unsymmetrical Dialkyl Polysulfides . . . . . . . . . . . . . . . . . 584


39.10.7.1.1 Method 1: Reaction of Thiols with N-(Methyldisulfanyl)phthalimide . . . . . 58539.10.7.1.2 Method 2: Reaction of Alkyl Chloro Trisulfides with Alkenes . . . . . . . . . . . . . 586

39.11 Product Class 11: Thiiranes and DerivativesM. Saito and J. Nakayama

39.11 Product Class 11: Thiiranes and Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 589

39.11.1 Product Subclass 1: Thiirane 1,1-Dioxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 589


39.11.1.1.1 Method 1: Oxidation of Thiiranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58939.11.1.1.2 Method 2: Base-Promoted Cyclizations of Sulfones . . . . . . . . . . . . . . . . . . . . . 59039.11.1.1.3 Method 3: Synthesis of Symmetrical Thiirane 1,1-Dioxides by the

Dimerization of Alkanesulfonyl Chlorides . . . . . . . . . . . . . . . . . . . 59239.11.1.1.4 Method 4: Synthesis from Thiocarbonyl Compounds and Diazoalkanes . . 59239.11.1.1.5 Method 5: Reduction of Thiirene 1,1-Dioxides . . . . . . . . . . . . . . . . . . . . . . . . . . 595

39.11.2 Product Subclass 2: Thiirane 1-Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 595


39.11.2.1.1 Method 1: Oxidation of Thiiranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59539.11.2.1.2 Method 2: Metal-Catalyzed Sulfinyl Transfer to Alkenes . . . . . . . . . . . . . . . . 597

39.11.3 Product Subclass 3: Thiiranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 598


39.11.3.1.1 Method 1: Synthesis from Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59839.11.3.1.1.1 Variation 1: Sulfuration with Sulfur, Sulfur Dichloride, or Sulfenyl Halides . 59839.11.3.1.1.2 Variation 2: Sulfuration with 1,2,3,4-Thiatriazoles . . . . . . . . . . . . . . . . . . . . . . . 60239.11.3.1.1.3 Variation 3: Sulfuration with Sulfines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60339.11.3.1.1.4 Variation 4: Sulfuration by Metal-Catalyzed Sulfur Transfer . . . . . . . . . . . . . . 605

XXXII Table of Contents


39.11.3.1.2 Method 2: Synthesis from Oxiranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60639.11.3.1.2.1 Variation 1: Ammonium Cerium(IV) Nitrate Catalyzed Sulfuration Using

Ammonium Thiocyanate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60639.11.3.1.2.2 Variation 2: Ruthenium (or Aluminum, Tin, or Manganese) Catalyzed

Sulfurations Using Ammonium Thiocyanate . . . . . . . . . . . . . . . . . 60739.11.3.1.2.3 Variation 3: Titanium-Catalyzed Sulfuration Using Ammonium

Thiocyanate or Thiourea as the Sulfur Source . . . . . . . . . . . . . . . . 60739.11.3.1.2.4 Variation 4: Sulfurations Using Ammonium Thiocyanate or Thiourea in

Reactions Catalyzed by Other Metal Salts . . . . . . . . . . . . . . . . . . . 60839.11.3.1.2.5 Variation 5: Sulfuration Using Polymer- or Solid-Supported Reagents or

Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61239.11.3.1.2.6 Variation 6: Sulfuration in Water Using Cyclodextrins . . . . . . . . . . . . . . . . . . . . 61439.11.3.1.2.7 Variation 7: Sulfuration Using Potassium Thiocyanate in Ionic Liquids . . . . 61539.11.3.1.2.8 Variation 8: Sulfuration Using Thiourea Catalyzed by Silica Gel . . . . . . . . . . . 61639.11.3.1.2.9 Variation 9: Sulfuration Using Potassium Thiocyanate in a Low-Hydrated

Solid–Liquid Heterogeneous Medium . . . . . . . . . . . . . . . . . . . . . . . 61739.11.3.1.2.10 Variation 10: Sulfuration Using Thiourea without a Solvent . . . . . . . . . . . . . . . 61839.11.3.1.2.11 Variation 11: Sulfuration with Phosphine Sulfides . . . . . . . . . . . . . . . . . . . . . . . . . 61939.11.3.1.2.12 Variation 12: Sulfuration with Dimethylthioformamide . . . . . . . . . . . . . . . . . . . 62039.11.3.1.2.13 Variation 13: Sulfuration with 3-Methylbenzothiazole-2(3H)-thione . . . . . . . 62139.11.3.1.2.14 Variation 14: Sulfuration with Elemental Sulfur or Phosphorus Pentasulfide

under Microwave Irradiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62139.11.3.1.3 Method 3: Synthesis from Thiocarbonyl Compounds . . . . . . . . . . . . . . . . . . . 62239.11.3.1.3.1 Variation 1: From Thioketones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62339.11.3.1.3.2 Variation 2: From Thioaldehydes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63539.11.3.1.3.3 Variation 3: From Thioketone S-Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63639.11.3.1.4 Method 4: Synthesis from Haloalkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63739.11.3.1.5 Method 5: Synthesis from b-Hydroxylated Thiols . . . . . . . . . . . . . . . . . . . . . . . 63839.11.3.1.6 Method 6: Synthesis from Sulfides as Thiolate Precursors . . . . . . . . . . . . . . . 64039.11.3.1.6.1 Variation 1: From Thiophosphates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64039.11.3.1.6.2 Variation 2: From Cyclic Xanthates or Their Equivalents . . . . . . . . . . . . . . . . . 64339.11.3.1.6.3 Variation 3: From 2-(Alkylsulfanyl)-4,4-dimethyl-4,5-dihydrooxazoles or

Thiazoles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64539.11.3.1.6.4 Variation 4: From Pyridyl Sulfides, Dithiocarbamates, or Dithiocarbonates 64639.11.3.1.7 Method 7: Synthesis from Heterocyclic Compounds . . . . . . . . . . . . . . . . . . . 647


39.11.3.2.1 Method 1: Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64939.11.3.2.2 Method 2: Alkene Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64939.11.3.2.3 Method 3: Thiiranes as Sulfuration Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . 65039.11.3.2.4 Method 4: Thiiranes as 1,3-Dipoles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 651

39.11.4 Product Subclass 4: Thiiranium Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 651


39.11.4.1.1 Method 1: Synthesis from Thiiranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65139.11.4.1.2 Method 2: Synthesis from Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 652

Table of Contents XXXIII


39.12 Product Class 12: Thietanes, 1,2-Oxathietanes, and DerivativesE. Block

39.12 Product Class 12: Thietanes, 1,2-Oxathietanes, and Derivatives . . . . . . . . . . 659

39.12.1 Product Subclass 1: Thietanes and DerivativesE. Block

39.12.1 Product Subclass 1: Thietanes and Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . 661

39.12.1.1 Thietanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 662

39.12.1.1.1 Synthesis of Thietanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 662

39.12.1.1.1.1 Synthesis by Ring-Closure Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 662

39.12.1.1.1.1.1 By Formation of Two S—C Bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 662

39.12.1.1.1.1.1.1 Method 1: Reaction of 1,3-Dihalides or 1,3-Disulfonates with Sulfide Ion 66239.12.1.1.1.1.1.2 Method 2: Reaction of Dienes with Sulfur Compounds . . . . . . . . . . . . . . . . . 66439.12.1.1.1.1.1.2.1 Variation 1: Addition of Elemental Sulfur . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66439.12.1.1.1.1.1.2.2 Variation 2: Addition of Sulfur Dichloride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66439.12.1.1.1.1.1.3 Method 3: Reaction of Ketones with Sulfur Dichloride . . . . . . . . . . . . . . . . . . 66539.12.1.1.1.1.1.4 Method 4: Reaction of Ammonium Hydrosulfide with

3-Adamantan-2-ylidene-1,1,1-trifluoropropan-2-one . . . . . . . . . 665

39.12.1.1.1.1.2 By Formation of One S—C and One C—C Bond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 665

39.12.1.1.1.1.2.1 Method 1: Photochemical or Thermal Cycloaddition of ThiocarbonylCompounds and Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 665

39.12.1.1.1.1.2.1.1 Variation 1: Intermolecular Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66539.12.1.1.1.1.2.1.2 Variation 2: Intermolecular Processes Involving Metal Complexes of

Thioaldehydes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66739.12.1.1.1.1.2.1.3 Variation 3: Intramolecular Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66739.12.1.1.1.1.2.2 Method 2: Reaction of Thiones with Quadricyclane . . . . . . . . . . . . . . . . . . . . 669

39.12.1.1.1.1.3 By Formation of One S—C Bond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 670

39.12.1.1.1.1.3.1 Method 1: Synthesis from 1-Halo-3-sulfanylpropanes,3-Sulfanylpropanols, and Related Compounds . . . . . . . . . . . . . . . 670

39.12.1.1.1.1.3.1.1 Variation 1: 2-(Chloromethyl)oxirane-Related Systems . . . . . . . . . . . . . . . . . . 67339.12.1.1.1.1.3.1.2 Variation 2: Nucleophile-Induced Cyclization of O,O-Diethyl

S-(1,3-Diaryl-3-oxopropyl) Phosphorodithioates . . . . . . . . . . . . . 67639.12.1.1.1.1.3.2 Method 2: Intramolecular Sulfenyl Bromide–Alkene Addition . . . . . . . . . . . 677

39.12.1.1.1.2 Synthesis by Ring Transformation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 677

39.12.1.1.1.2.1 Method 1: Ring Enlargement of Thiiranes and Derivatives . . . . . . . . . . . . . . 67739.12.1.1.1.2.1.1 Variation 1: From 2-(Chloromethyl)thiirane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67739.12.1.1.1.2.1.2 Variation 2: From Thiirane Alcohols under Mitsunobu Conditions . . . . . . . . 67739.12.1.1.1.2.1.3 Variation 3: From Thiiranes and 3-Chloroallyllithium . . . . . . . . . . . . . . . . . . . . . 67839.12.1.1.1.2.2 Method 2: Ring Contraction by Desulfurization of 1,2-Dithiolanes . . . . . . . 67839.12.1.1.1.2.3 Method 3: Ring Contraction of Diazothiolanones by Wolff

Rearrangement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67839.12.1.1.1.2.4 Method 4: Ring Contraction–Rearrangement of Penams . . . . . . . . . . . . . . . 679

XXXIV Table of Contents


39.12.1.1.1.2.5 Method 5: Ring Contraction–Rearrangement of 4-(Iodomethyl)-4,5-dihydrothiazolium Salts with Base . . . . . . . . . . . . . . . . . . . . . . 679

39.12.1.1.1.2.6 Method 6: Synthesis from 1,3-Dioxan-2-ones . . . . . . . . . . . . . . . . . . . . . . . . . . 68039.12.1.1.1.2.7 Method 7: Ring Contraction on Photolysis of 2H-Thiopyran-3(6H)-ones . 680

39.12.1.1.1.3 Synthesis by Substituent Modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 681

39.12.1.1.1.3.1 Substitution of Existing Substituents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 681

39.12.1.1.1.3.1.1 Of Hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 681

39.12.1.1.1.3.1.1.1 Method 1: Direct Free-Radical Acetoxylation of Thietanes . . . . . . . . . . . . . . 68139.12.1.1.1.3.1.1.2 Method 2: Replacement of Hydrogen with Nitrogen Heterocycles . . . . . . 681

39.12.1.1.1.3.1.2 Of Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 683

39.12.1.1.1.3.1.2.1 Method 1: Desilylation with Tetrabutylammonium Fluoride . . . . . . . . . . . . 683

39.12.1.1.1.3.1.3 Of Oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 683

39.12.1.1.1.3.1.3.1 Method 1: Formation of 3-Alkylidenethietanes . . . . . . . . . . . . . . . . . . . . . . . . . 68339.12.1.1.1.3.1.3.2 Method 2: Formation of Hydrazones and Diazo Compounds . . . . . . . . . . . . 68339.12.1.1.1.3.1.3.3 Method 3: Reductive Amination via the Leuckart Reaction . . . . . . . . . . . . . . 684

39.12.1.1.1.3.2 Addition Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 684

39.12.1.1.1.3.2.1 Method 1: Reduction with Lithium Aluminum Hydride or SodiumBorohydride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 684

39.12.1.1.1.3.2.2 Method 2: Cycloaddition Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 685

39.12.1.1.1.3.3 Modification of Substituents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 685

39.12.1.1.1.3.3.1 Method 1: Oxidation of Thietan-3-ol to Thietan-3-one . . . . . . . . . . . . . . . . . . 68539.12.1.1.1.3.3.2 Method 2: Reduction of Thietane 1-Oxide and 1,1-Dioxide to Thietane . . 685

39.12.1.1.2 Applications of Thietanes in Organic Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 686

39.12.1.1.2.1 Method 1: Electrophile-Induced Ring Opening . . . . . . . . . . . . . . . . . . . . . . . . . 68639.12.1.1.2.2 Method 2: Regiospecific Carbonylation and Ring Expansion of Thietanes 68739.12.1.1.2.3 Method 3: Synthesis of Isothiazolidines by Reaction of Nitrenes with

Thietanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 687

39.12.1.2 Thietane 1-Oxides and Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 688

39.12.1.2.1 Synthesis by Ring-Closure Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 688

39.12.1.2.1.1 By Formation of One S—C and One C—C Bond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 688

39.12.1.2.1.2 By Formation of One S—C Bond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 688

39.12.1.2.1.2.1 Method 1: Intramolecular Cycloaddition of Sulfenic Acid to Alkenes . . . . . 688

39.12.1.2.2 Synthesis by Addition Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 689

39.12.1.2.2.1 Addition of Heteroatoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 689

39.12.1.2.2.1.1 Method 1: S-Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68939.12.1.2.2.1.2 Method 2: S-Amidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 690

39.12.1.2.3 Rearrangement of Substituents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 690

39.12.1.2.3.1 Method 1: Isomerization of Thietane Sulfoxides . . . . . . . . . . . . . . . . . . . . . . . . 690

39.12.1.3 Thietane 1,1-Dioxides and Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 691


Table of Contents XXXV


39.12.1.3.1.1 By Formation of Two S—C Bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 691

39.12.1.3.1.1.1 Method 1: Addition of Sulfur Dioxide to Dienes . . . . . . . . . . . . . . . . . . . . . . . . 691

39.12.1.3.1.2 By Formation of One S—C and One C—C Bond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 691

39.12.1.3.1.2.1 Method 1: Addition of Sulfenes to Unsaturated Compounds . . . . . . . . . . . . 691

39.12.1.3.1.3 By Formation of One C—C Bond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 693

39.12.1.3.1.3.1 Method 1: Base-Catalyzed Cyclization of Haloalkyl Sulfones . . . . . . . . . . . . 693

39.12.1.3.2 Synthesis by Ring Transformation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 694

39.12.1.3.2.1 Method 1: Photochemical Insertion of Sulfur Dioxide into Cyclopropanes 69439.12.1.3.2.2 Method 2: Photoinduced Rearrangement of 8-Thia-1-aza-

bicyclo[4.2.1]nona-2,4-diene 8,8-Dioxide . . . . . . . . . . . . . . . . . . . 695

39.12.1.3.3 Synthesis by Substituent Modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 695

39.12.1.3.3.1 Substitution of Existing Substituents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 695

39.12.1.3.3.1.1 Of Hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 695

39.12.1.3.3.1.1.1 Method 1: Hydrogen–Deuterium Exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69539.12.1.3.3.1.1.2 Method 2: Lithiation of Thietane 1,1-Dioxides . . . . . . . . . . . . . . . . . . . . . . . . . . 69539.12.1.3.3.1.1.3 Method 3: Direct Free-Radical Halogenation of Thietane 1,1-Dioxides . . . 696

39.12.1.3.3.1.2 Of Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 696

39.12.1.3.3.1.2.1 Method 1: Replacement of Metals by Carbon and Other Elements . . . . . . 69639.12.1.3.3.1.2.2 Method 2: Replacement of Lithium by Halogen . . . . . . . . . . . . . . . . . . . . . . . . 697

39.12.1.3.3.1.3 Of Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 697

39.12.1.3.3.1.3.1 Method 1: Replacement of an Acyl Group in a-Acylthietane 1,1-Dioxideswith Bromine or Iodine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 697

39.12.1.3.3.1.4 Of Oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 698

39.12.1.3.3.1.4.1 Method 1: Formation of Thietane-3-thione 1,1-Dioxides,Thietane-3-spirothiirane 1,1-Dioxides, and3-Alkylidenethietane 1,1-Dioxides . . . . . . . . . . . . . . . . . . . . . . . . . . 698

39.12.1.3.3.2 Addition Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 698

39.12.1.3.3.2.1 Method 1: Reduction by Catalytic Hydrogenation or with SodiumBorohydride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 698

39.12.1.3.3.2.2 Method 2: Addition of Organic Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69939.12.1.3.3.2.2.1 Variation 1: Cycloaddition of 1,3-Dienes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69939.12.1.3.3.2.2.2 Variation 2: 1,3-Dipolar Cycloaddition of Diazoalkanes to Thiete

1,1-Dioxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69939.12.1.3.3.2.2.3 Variation 3: Addition of Carbanions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70039.12.1.3.3.2.3 Method 3: Addition of Heteroatoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70139.12.1.3.3.2.3.1 Variation 1: Addition of Halogens to Thiete 1,1-Dioxides . . . . . . . . . . . . . . . . . 70139.12.1.3.3.2.3.2 Variation 2: Addition of Oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70139.12.1.3.3.2.3.3 Variation 3: Addition of a,w-Dithiols to Thiete 1,1-Dioxides . . . . . . . . . . . . . . 70339.12.1.3.3.2.3.4 Variation 4: Addition of Amines to 2-Methylenethiete 1,1-Dioxides . . . . . . . 703

39.12.1.4 Sulfonium and Oxosulfonium Salts and Their Ylides . . . . . . . . . . . . . . . . . . . . . . . . . 703


XXXVI Table of Contents


39.12.1.4.1.1 By Formation of One S—C Bond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 703

39.12.1.4.1.1.1 Method 1: Cyclization of 1-Diazoalkyl 1-Sulfanylmethyl Ketones . . . . . . . . 703

39.12.1.4.2 Synthesis by Ring Transformation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 704

39.12.1.4.2.1 Method 1: Ring Expansion of Thiiranes and Derivatives . . . . . . . . . . . . . . . . . 704

39.12.1.4.3 Addition Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 705

39.12.1.4.3.1 Addition of Organic Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 705

39.12.1.4.3.1.1 Method 1: S-Alkylation of Thietanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70539.12.1.4.3.1.2 Method 2: O-Alkylation of Thietane 1-Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . 705

39.12.1.4.3.2 Addition of Heteroatoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 706

39.12.1.4.3.2.1 Method 1: S-Amination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 706

39.12.2 Product Subclass 2: 1,2-Oxathietanes and DerivativesJ. Drabowicz and J. Lewkowski

39.12.2 Product Subclass 2: 1,2-Oxathietanes and Derivatives . . . . . . . . . . . . . . . . . . . 711

39.12.2.1 1,2-Oxathietanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 711

39.12.2.1.1 Synthesis of 1,2-Oxathietanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 711

39.12.2.1.1.1 Method 1: Diazotization of 2-[(2-Chloroethyl)sulfinyl]ethylamine . . . . . . . 71139.12.2.1.1.2 Method 2: Thermolysis of 1-{2-[(2-Chloroethyl)sulfinyl]ethyl}-

1-nitrosourea Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 712

39.12.2.1.2 Applications of 1,2-Oxathietanes in Organic Synthesis . . . . . . . . . . . . . . . . . . . . . . . 713

39.12.2.1.2.1 Method 1: Cycloreversion of 1,2-Oxathietanes to Thioacetone . . . . . . . . . . 713

39.12.2.2 1,2-Oxathietane 2-Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 714

39.12.2.2.1 Synthesis of 1,2-Oxathietane 2-Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 714

39.12.2.2.1.1 Method 1: Photolysis of Sulfolane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71439.12.2.2.1.2 Method 2: Reaction of Sulfur Dioxide with Ketene Derivatives . . . . . . . . . . 71439.12.2.2.1.3 Method 3: Reaction of Sulfuryl Chloride with b-Hydroxy Sulfoxides . . . . . 71539.12.2.2.1.4 Method 4: Reaction of Sulfur Dioxide with Quadricyclane . . . . . . . . . . . . . . . 716

39.12.2.2.2 Applications of 1,2-Oxathietane 2-Oxides in Organic Synthesis . . . . . . . . . . . . . . 716

39.12.2.2.2.1 Method 1: Thermal Decomposition and Rearrangement Reactions of1,2-Oxathietane 2-Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 716

39.12.2.3 1,2-Oxathietane 2,2-Dioxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 717

39.12.2.3.1 Synthesis of 1,2-Oxathietane 2,2-Dioxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 717

39.12.2.3.1.1 Method 1: Cycloaddition of Sulfur Trioxide and Alkenes . . . . . . . . . . . . . . . . 71739.12.2.3.1.2 Method 2: Reactions of Alkanesulfonyl Chlorides with Carbonyl

Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71939.12.2.3.1.3 Method 3: Modification of Remote Functionalities in 1,2-Oxathietane

2,2-Dioxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 720

39.12.2.3.2 Applications of 1,2-Oxathietane 2,2-Dioxides in Organic Synthesis . . . . . . . . . . . 721

39.12.2.3.2.1 Method 1: Rearrangement and Isomerization Reactions . . . . . . . . . . . . . . . . 72139.12.2.3.2.2 Method 2: Nucleophilic Attack at the Ring Sulfur Atom . . . . . . . . . . . . . . . . . 722

Table of Contents XXXVII


39.12.2.3.2.3 Method 3: Electrophilic Attack at the Ring Oxygen Atom . . . . . . . . . . . . . . . 72339.12.2.3.2.4 Method 4: Elimination Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 724

39.12.3 Product Subclass 3: 1,2-Dithietanes, 1,2-Thiazetidines, 1,2-Thiaphos-phetanes, and Derivatives of Various Oxidation StatesN. Kambe

39.12.3 Product Subclass 3: 1,2-Dithietanes, 1,2-Thiazetidines, 1,2-Thiaphos-phetanes, and Derivatives of Various Oxidation States . . . . . . . . . . . . . . . . . . . 727


39.12.3.1.1 Method 1: Synthesis of 1,2-Dithietanes and Derivatives . . . . . . . . . . . . . . . . 72739.12.3.1.1.1 Variation 1: Synthesis of 1,2-Dithietanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72739.12.3.1.1.2 Variation 2: Synthesis of 1,2-Dithietane 1,1-Dioxides . . . . . . . . . . . . . . . . . . . . 72839.12.3.1.2 Method 2: Synthesis of 1,2-Thiazetidines and Derivatives . . . . . . . . . . . . . . . 72839.12.3.1.2.1 Variation 1: Synthesis of 1,2-Thiazetidines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72839.12.3.1.2.2 Variation 2: Synthesis of 1,2-Thiazetidine 1-Oxides . . . . . . . . . . . . . . . . . . . . . . 72939.12.3.1.2.3 Variation 3: Synthesis of 1,2-Thiazetidine 1,1-Dioxides . . . . . . . . . . . . . . . . . . . 72939.12.3.1.2.4 Variation 4: Synthesis of 1,2-Thiazetidine 1-Imides . . . . . . . . . . . . . . . . . . . . . . 73039.12.3.1.3 Method 3: Synthesis of 1,2-Thiaphosphetanes . . . . . . . . . . . . . . . . . . . . . . . . . 730

39.13 Product Class 13: Thiolanes, Larger Rings, and Derivatives of VariousOxidation StatesR. Sato and T. Kimura

39.13 Product Class 13: Thiolanes, Larger Rings, and Derivatives of VariousOxidation States . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 733

39.13.1 Product Subclass 1: Cyclic Alkanesulfonic Acid DerivativesR. Sato and T. Kimura

39.13.1 Product Subclass 1: Cyclic Alkanesulfonic Acid Derivatives . . . . . . . . . . . . . . . 735


39.13.1.1.1 Cyclic Sulfonic Acid Esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 735

39.13.1.1.1.1 Method 1: Oxidation of a Cyclic Sulfinic Acid Ester . . . . . . . . . . . . . . . . . . . . . 73539.13.1.1.1.2 Method 2: Intramolecular Substitution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 735

39.13.1.1.2 Cyclic Thiosulfonic Acid S-Esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 736

39.13.1.1.2.1 Method 1: Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73639.13.1.1.2.1.1 Variation 1: Oxidation of Dithiols with Hydrogen Peroxide . . . . . . . . . . . . . . . 73639.13.1.1.2.1.2 Variation 2: Oxidation of Cyclic Disulfides with Potassium Periodate . . . . . . 73739.13.1.1.2.2 Method 2: Thiolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 737

39.13.1.1.3 Cyclic Sulfonic Acid Amides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 738

39.13.1.1.3.1 Method 1: Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73839.13.1.1.3.2 Method 2: Intramolecular Nucleophilic Substitution . . . . . . . . . . . . . . . . . . . . 73839.13.1.1.3.3 Method 3: Intramolecular Cycloaddition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73939.13.1.1.3.4 Method 4: Ring-Closing Metathesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 740

XXXVIII Table of Contents


39.13.1.1.3.5 Method 5: N-Arylation by Palladium-Catalyzed Cross Coupling . . . . . . . . . 741

39.13.2 Product Subclass 2: Cyclic Dialkyl Sulfones and DerivativesR. Sato and T. Kimura

39.13.2 Product Subclass 2: Cyclic Dialkyl Sulfones and Derivatives . . . . . . . . . . . . . . 745


39.13.2.1.1 Cyclic Sulfones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 745

39.13.2.1.1.1 Method 1: Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74539.13.2.1.1.1.1 Variation 1: With 3-Chloroperoxybenzoic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . 74539.13.2.1.1.1.2 Variation 2: With Hydrogen Peroxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74539.13.2.1.1.2 Method 2: Cheletropic Addition of Sulfur Dioxide to 1,3-Dienes . . . . . . . . . 746

39.13.2.1.2 Cyclic Sulfoximides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 746

39.13.2.1.2.1 Method 1: Imidation of Sulfoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74739.13.2.1.2.2 Method 2: N-Functionalization of a Sulfoximide . . . . . . . . . . . . . . . . . . . . . . . . 747

39.13.2.1.3 Cyclic Sulfonediimines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 748

39.13.2.1.3.1 Method 1: Diimidation of Sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74839.13.2.1.3.2 Method 2: N-Functionalization of Sulfonediimines . . . . . . . . . . . . . . . . . . . . . 748

39.13.3 Product Subclass 3: Cyclic Alkanesulfinic Acid DerivativesR. Sato and T. Kimura

39.13.3 Product Subclass 3: Cyclic Alkanesulfinic Acid Derivatives . . . . . . . . . . . . . . . . 751


39.13.3.1.1 Cyclic Sulfinic Acid Esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 751

39.13.3.1.1.1 Method 1: Oxidation of 3-Sulfanylpropan-1-ols . . . . . . . . . . . . . . . . . . . . . . . . 75139.13.3.1.1.2 Method 2: Rearrangement of Cyclic Sulfones . . . . . . . . . . . . . . . . . . . . . . . . . . 75139.13.3.1.1.3 Method 3: Oxidative Cyclization of Hydroxyalkyl Disulfides . . . . . . . . . . . . . 752

39.13.3.1.2 Cyclic Thiosulfinic Acid S-Esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 752

39.13.3.1.2.1 Method 1: Oxidation of Cyclic Disulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75239.13.3.1.2.1.1 Variation 1: With Hydrogen Peroxide/Formic Acid . . . . . . . . . . . . . . . . . . . . . . . 75239.13.3.1.2.1.2 Variation 2: With Potassium Periodate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75339.13.3.1.2.1.3 Variation 3: With 3-Chloroperoxybenzoic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . 75339.13.3.1.2.2 Method 2: Cycloaddition Reactions of Disulfur Monoxide . . . . . . . . . . . . . . . 754

39.13.3.1.3 Cyclic Sulfinic Acid Amides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 754

39.13.3.1.3.1 Method 1: Oxidation of Aminoalkanethiols . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75539.13.3.1.3.2 Method 2: N-Functionalization of Cyclic Sulfinamides . . . . . . . . . . . . . . . . . . 755

39.13.4 Product Subclass 4: Cyclic Dialkyl Sulfoxides and DerivativesJ. L. Garc4a-Ruano, M. B. Cid, A. M. Mart4n-Castro, and J. Alem8n

39.13.4 Product Subclass 4: Cyclic Dialkyl Sulfoxides and Derivatives . . . . . . . . . . . . 757


Table of Contents XXXIX


39.13.4.1.1 Cyclic Diheteroatom-Substituted l4-Sulfanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 757

39.13.4.1.2 Cyclic Sulfoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 758

39.13.4.1.2.1 Achiral and Racemic Cyclic Sulfoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 758

39.13.4.1.2.1.1 Method 1: Oxidation with Oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75939.13.4.1.2.1.1.1 Variation 1: Photochemical Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75939.13.4.1.2.1.1.2 Variation 2: Catalyzed by Metals or Organic Compounds . . . . . . . . . . . . . . . . 76039.13.4.1.2.1.2 Method 2: Oxidation with Hydrogen Peroxide . . . . . . . . . . . . . . . . . . . . . . . . . 76139.13.4.1.2.1.3 Method 3: Oxidation with Organic Peroxides . . . . . . . . . . . . . . . . . . . . . . . . . . 76539.13.4.1.2.1.4 Method 4: Oxidation with Peroxy Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76639.13.4.1.2.1.5 Method 5: Oxidation with Halogen Derivatives . . . . . . . . . . . . . . . . . . . . . . . . 76839.13.4.1.2.1.5.1 Variation 1: Using Molecular Halogens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76839.13.4.1.2.1.5.2 Variation 2: Using Periodates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76939.13.4.1.2.1.5.3 Variation 3: Using Periodic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77039.13.4.1.2.1.5.4 Variation 4: Using Hypervalent Iodine(III) Reagents . . . . . . . . . . . . . . . . . . . . . . 77039.13.4.1.2.1.5.5 Variation 5: Using Hypochlorites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77039.13.4.1.2.1.5.6 Variation 6: Using Chlorites, Bromites, and Bromates . . . . . . . . . . . . . . . . . . . . 77139.13.4.1.2.1.5.7 Variation 7: Using Chloramine-T and Bromamine-T . . . . . . . . . . . . . . . . . . . . . . 77139.13.4.1.2.1.6 Method 6: Oxidation with Nitrogen Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . 77139.13.4.1.2.1.6.1 Variation 1: Using Nitric Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77139.13.4.1.2.1.6.2 Variation 2: Using Nitrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77139.13.4.1.2.1.6.3 Variation 3: Using Other Nitrogen Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . 77239.13.4.1.2.1.7 Method 7: Oxidation with Metal Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . 77239.13.4.1.2.1.8 Method 8: Oxidation with Compounds Having a N—O Bond . . . . . . . . . . . . 77239.13.4.1.2.1.9 Method 9: Oxidation with Dimenthyl Selenoxide . . . . . . . . . . . . . . . . . . . . . . . 77239.13.4.1.2.1.10 Method 10: Oxidation with Sulfoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77339.13.4.1.2.1.11 Method 11: Electrochemical Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77339.13.4.1.2.1.12 Method 12: Cycloaddition Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77439.13.4.1.2.1.12.1 Variation 1: From Sulfur Monoxide by [4 + 1] or [6 + 1] Cycloaddition

with 1,3-Dienes or 1,3,5-Trienes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77439.13.4.1.2.1.12.2 Variation 2: From Thioketone S-Oxides by [3 + 2] Cycloaddition . . . . . . . . . . 77439.13.4.1.2.1.12.3 Variation 3: From Thioaldehyde and Thioketone S-Oxides by Diels–Alder

Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77539.13.4.1.2.1.12.4 Variation 4: From Thiophene S-Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77739.13.4.1.2.1.13 Method 13: Cyclization via Anionic Intermediates . . . . . . . . . . . . . . . . . . . . . . . 77739.13.4.1.2.1.13.1 Variation 1: Intramolecular Nucleophilic Addition . . . . . . . . . . . . . . . . . . . . . . . 77739.13.4.1.2.1.13.2 Variation 2: Intermolecular Nucleophilic Reactions . . . . . . . . . . . . . . . . . . . . . . 77839.13.4.1.2.1.14 Method 14: Radical Cyclization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77939.13.4.1.2.1.15 Methods 15: Miscellaneous Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 779

39.13.4.1.2.2 Optically Active Cyclic Sulfoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 782

39.13.4.1.2.2.1 Method 1: Oxidation with Achiral Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78239.13.4.1.2.2.2 Method 2: Oxidation with Alkyl Peroxides and Chiral Metal Catalysts . . . . 78439.13.4.1.2.2.2.1 Variation 1: Monooxidation of 1,3-Dithiolanes and 1,3-Dithianes Using

tert-Butyl Hydroperoxide, Titanium(IV) Isopropoxide, and(R,R)-Diethyl Tartrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 784

39.13.4.1.2.2.2.2 Variation 2: Dioxidation of 1,3-Dithiolanes and 1,3-Dithianes withTitanium(IV) Isopropoxide and (R,R)-Diethyl Tartrate . . . . . . . . . 788

XL Table of Contents


39.13.4.1.2.2.2.3 Variations 3: Other Variations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78939.13.4.1.2.2.3 Method 3: Oxidation Using Other Chiral Reagents . . . . . . . . . . . . . . . . . . . . . 79139.13.4.1.2.2.4 Method 4: Biological Oxidations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79239.13.4.1.2.2.5 Method 5: Resolution of Racemic Mixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . . 795

39.13.4.1.3 Cyclic Sulfimides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 795

39.13.4.1.3.1 Optically Inactive Cyclic Sulfimides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 796

39.13.4.1.3.1.1 Method 1: Oxidative Amination of Sulfides with N-Halo Derivatives . . . . . 79639.13.4.1.3.1.1.1 Variation 1: Synthesis of N-Sulfonylsulfimides . . . . . . . . . . . . . . . . . . . . . . . . . . . 79639.13.4.1.3.1.1.2 Variation 2: Synthesis of N-Alkyl- and N-Arylsulfimides . . . . . . . . . . . . . . . . . . 79739.13.4.1.3.1.1.3 Variation 3: Synthesis of N-Acylsulfimides and Derivatives . . . . . . . . . . . . . . . 79839.13.4.1.3.1.2 Method 2: Amination of Sulfoxides with Compounds Containing an

Amino Group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79939.13.4.1.3.1.3 Method 3: Synthesis of N-Unsubstituted Sulfimides . . . . . . . . . . . . . . . . . . . . 799

39.13.4.1.3.2 Optically Active Cyclic Sulfimides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 800


39.13.4.2.1 Applications of Sulfimides in Organic Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 800

39.13.4.2.1.1 Method 1: Synthesis of Sulfides by Reduction of Cyclic Sulfimides . . . . . . . 80039.13.4.2.1.2 Method 2: Synthesis of Sulfoximides by Oxidative Amination of Cyclic

Sulfimides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80139.13.4.2.1.3 Method 3: Synthesis of Ketene Dithioacetals from Cyclic Sulfimides . . . . . 80139.13.4.2.1.4 Method 4: Synthesis of Heterocycles via Nitrene Intermediates by

Photolysis or Thermolysis of Cyclic Sulfimides . . . . . . . . . . . . . . . 802

39.13.5 Product Subclass 5: Cyclic Alkanethiolates of Group 1, 2, and 13–15MetalsN. Kambe

39.13.5 Product Subclass 5: Cyclic Alkanethiolates of Group 1, 2, and 13–15 Metals 811


39.13.5.1.1 Method 1: Synthesis of Dithiametallacycles . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81139.13.5.1.2 Method 2: Coordination of Dithiaalkanes to Metals . . . . . . . . . . . . . . . . . . . . 81139.13.5.1.3 Method 3: Dimerization of Metal Thiolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81239.13.5.1.4 Method 4: Addition to C=S or Si=S Bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81239.13.5.1.5 Method 5: Transmetalation of Cyclic Metal Alkanethiolates . . . . . . . . . . . . . 812

39.13.6 Product Subclass 6: Cyclic Alkanethiolates of Group 3–12 MetalsA. Polo and J. Real

39.13.6 Product Subclass 6: Cyclic Alkanethiolates of Group 3–12 Metals . . . . . . . . . 813


39.13.6.1.1 Method 1: Reactions of Metal Halides with an Alkanethiol, with anAlkanethiol and Base, or with a Main Group Alkanethiolate . . 813

39.13.6.1.1.1 Variation 1: Reactions between a Metal Complex and an Alkanethiol . . . . . 81339.13.6.1.1.2 Variation 2: Reaction of a Metal Complex with an Alkanethiol and a Base . 81539.13.6.1.1.3 Variation 3: Reactions of Metal Complexes with Main Group Alkanethio-

lates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 816

Table of Contents XLI


39.13.6.1.2 Method 2: Reactions between Basic Ligand Complexes and Alkanethiolswith the Displacement of a Protonated Ligand . . . . . . . . . . . . . . 818

39.13.6.1.3 Method 3: Reactions of Alkanethiols with Metal Complexes underReducing Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 819

39.13.6.1.3.1 Variation 1: Reduction of the Metal by an Added Reducing Agent . . . . . . . . 81939.13.6.1.3.2 Variation 2: Reduction of the Metal by an Excess of an Alkanethiol or a

Phosphinethiol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82039.13.6.1.4 Method 4: Reaction of Coordinated Sulfides with Electrophiles . . . . . . . . . 82139.13.6.1.5 Method 5: Oxidative Addition of an Alkanethiol or a Dialkyl Disulfide

to a Metal Complex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82239.13.6.1.5.1 Variation 1: Oxidative Addition of an Alkanethiol to a Metal Complex . . . . 82239.13.6.1.5.2 Variation 2: Oxidative Addition of a Dialkyl Disulfide to a Metal Complex . 82439.13.6.1.6 Method 6: Reaction of an Alkanethiolate–Metal Complex with a Second

Metal Complex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82439.13.6.1.7 Methods 7: Miscellaneous Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 825


39.13.6.2.1 Method 1: Catalytic Carbonylation Reactions with Cyclic Alkanethiolatesas Catalyst Precursors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 826

39.13.6.2.2 Method 2: Catalytic Asymmetric Organozinc Additions to Aldehydes . . . . 828

39.13.7 Product Subclass 7: Cyclic Dialkyl SulfidesM. Segi

39.13.7 Product Subclass 7: Cyclic Dialkyl Sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 833


39.13.7.1.1 Method 1: Synthesis from Metal Sulfides or Thiols . . . . . . . . . . . . . . . . . . . . . 83339.13.7.1.1.1 Variation 1: By Substitution with Dihalides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83339.13.7.1.1.2 Variation 2: By Substitution with Disulfonates . . . . . . . . . . . . . . . . . . . . . . . . . . . 83439.13.7.1.1.3 Variation 3: By Substitution with Cyclic Ammonium Salts . . . . . . . . . . . . . . . . 83639.13.7.1.1.4 Variation 4: By Addition to Enones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83639.13.7.1.1.5 Variation 5: By Reaction with Dioxiranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83739.13.7.1.2 Method 2: Synthesis from Acyclic Sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83739.13.7.1.2.1 Variation 1: By Dieckmann Condensation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83739.13.7.1.2.2 Variation 2: By Henry Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83839.13.7.1.3 Method 3: Synthesis from Dialkyl Disulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . 83939.13.7.1.3.1 Variation 1: By Addition to Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83939.13.7.1.3.2 Variation 2: By Radical Cyclization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83939.13.7.1.3.3 Variation 3: By Desulfurization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84039.13.7.1.4 Method 4: Synthesis from Sulfur Dichloride by Addition to Dienes . . . . . . 84139.13.7.1.5 Method 5: Synthesis from Vinylthiiranes by Ring Expansion . . . . . . . . . . . . . 84139.13.7.1.6 Method 6: Synthesis from Cyclic Sulfonium Salts . . . . . . . . . . . . . . . . . . . . . . . 84239.13.7.1.6.1 Variation 1: By Debenzylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84239.13.7.1.6.2 Variation 2: By Ring Expansion via Reductive Bond Cleavage . . . . . . . . . . . . . 84339.13.7.1.6.3 Variation 3: By [2,3]-Sigmatropic Rearrangement via Cyclic Sulfonium

Ylides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84339.13.7.1.7 Method 7: Synthesis from Thioaldehydes or Thioketones by [4 + 2]

Cycloaddition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 844

XLII Table of Contents


39.13.7.1.8 Method 8: Synthesis from Thiocarbonyl Ylides by 1,3-DipolarCycloaddition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 845


39.13.7.2.1 Method 1: Use as Organocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84539.13.7.2.1.1 Variation 1: Asymmetric Synthesis of Epoxides from Aldehydes . . . . . . . . . . 84539.13.7.2.1.2 Variation 2: Asymmetric Synthesis of Aziridines from Imines . . . . . . . . . . . . . 846

39.13.8 Product Subclass 8: Cyclic Trialkyloxosulfonium and TrialkylsulfoniumSalts and DerivativesY. Tang and X.-L. Sun

39.13.8 Product Subclass 8: Cyclic Trialkyloxosulfonium and TrialkylsulfoniumSalts and Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 851


39.13.8.1.1 Cyclic Trialkyloxosulfonium Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 851

39.13.8.1.1.1 Method 1: Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85139.13.8.1.1.2 Method 2: Anion Exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 852

39.13.8.1.2 Cyclic Trialkylsulfonium Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 852

39.13.8.1.2.1 Method 1: Alkylation of Cyclic Sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85339.13.8.1.2.1.1 Variation 1: With Halides and Related Reagents . . . . . . . . . . . . . . . . . . . . . . . . . 85339.13.8.1.2.1.2 Variation 2: With Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86339.13.8.1.2.1.3 Variation 3: With Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86539.13.8.1.2.1.4 Variation 4: With Ketones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86739.13.8.1.2.1.5 Variation 5: With Ethers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86739.13.8.1.2.1.6 Variation 6: With Diazo Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86839.13.8.1.2.2 Method 2: Ring-Closure Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86839.13.8.1.2.2.1 Variation 1: From Acyclic Sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86839.13.8.1.2.2.2 Variation 2: From Thiols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86939.13.8.1.2.2.3 Variation 3: From Alkanesulfenyl Halides and Related Compounds . . . . . . . 87039.13.8.1.2.2.4 Variation 4: From Sulfoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87139.13.8.1.2.3 Method 3: Reaction of Dialkylhalosulfonium Salts . . . . . . . . . . . . . . . . . . . . . . 87139.13.8.1.2.4 Method 4: Transformation of Cyclic Sulfonium Ylides . . . . . . . . . . . . . . . . . . . 87239.13.8.1.2.4.1 Variation 1: With Brønsted Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87239.13.8.1.2.4.2 Variation 2: With Alkylating Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87239.13.8.1.2.5 Method 5: Reaction of Cyclic Sulfanylsulfonium Salts with Alkenes . . . . . . 87339.13.8.1.2.6 Method 6: Transformation of Cyclic Sulfonium Salts . . . . . . . . . . . . . . . . . . . . 87439.13.8.1.2.6.1 Variation 1: By Anion Exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87439.13.8.1.2.6.2 Variation 2: By Modification of Remote Functional Groups . . . . . . . . . . . . . . . 875

39.13.9 Product Subclass 9: Cyclic Alkanesulfenic Acid DerivativesT. Wirth

39.13.9 Product Subclass 9: Cyclic Alkanesulfenic Acid Derivatives . . . . . . . . . . . . . . . 879


39.13.9.1.1 Cyclic Alkanesulfenic Acid Derivatives with a S—O Bond . . . . . . . . . . . . . . . . . . . . . 879

Table of Contents XLIII


39.13.9.1.1.1 Method 1: Synthesis of Oxathiolanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 879

39.13.9.1.2 Cyclic Alkanesulfenic Acid Derivatives with a S—N Bond . . . . . . . . . . . . . . . . . . . . . 879

39.13.9.1.2.1 Method 1: Synthesis of 3,6-Dihydro-2H-1,2-thiazines and1,2-Thiazinanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 880

39.13.9.1.2.2 Method 2: Synthesis of 4,5-Dihydroisothiazoles, Dihydrothiadiazoles,and Larger Heterocycles Containing a S—N Bond . . . . . . . . . . . . 880

39.13.9.1.3 Cyclic Alkanesulfenic Acid Derivatives with a S—P Bond . . . . . . . . . . . . . . . . . . . . . . 881

39.13.9.1.3.1 Method 1: Synthesis of 1,3,2-Thiazaphospholidines and1,3,2-Oxathiaphospholanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 881

39.13.10 Product Subclass 10: Cyclic Dialkyl Di- and PolysulfidesR. Sato and T. Kimura

39.13.10 Product Subclass 10: Cyclic Dialkyl Di- and Polysulfides . . . . . . . . . . . . . . . . . . 885


39.13.10.1.1 Cyclic Disulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 885

39.13.10.1.1.1 1,2-Dithiolanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 886

39.13.10.1.1.1.1 Method 1: Preparation from a Diol Using Sodium Tetrasulfide . . . . . . . . . . 88639.13.10.1.1.1.2 Method 2: Oxidation of a Dithiol Using Oxygen . . . . . . . . . . . . . . . . . . . . . . . . 88639.13.10.1.1.1.3 Method 3: Oxidation of a Dithiol Using Iodine . . . . . . . . . . . . . . . . . . . . . . . . . 887

39.13.10.1.1.2 1,2-Dithianes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 888

39.13.10.1.1.2.1 Method 1: Oxidation of a Dithiol Using Sulfur in Liquid Ammonia . . . . . . . 88839.13.10.1.1.2.2 Method 2: Oxidation of a Thiol Using Bis(1H-benzimidazol-1-yl) Sulfide . 88939.13.10.1.1.2.3 Method 3: Oxidation of a Dithiol Using Oxygen . . . . . . . . . . . . . . . . . . . . . . . . 889

39.13.10.1.1.3 3,6-Dihydro-1,2-dithiins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 890

39.13.10.1.1.3.1 Method 1: Reaction of a 1,3-Diene with Sulfur . . . . . . . . . . . . . . . . . . . . . . . . . 89039.13.10.1.1.3.2 Method 2: Oxidation of a Dithiol Using Iron(III) Chloride . . . . . . . . . . . . . . . . 89039.13.10.1.1.3.3 Method 3: Diels–Alder Reaction of 1,3-Dienes with a 1,2-Dithietane . . . . 89139.13.10.1.1.3.4 Method 4: Oxidation of a Dithiol Using Manganese(IV) Oxide . . . . . . . . . . . 891

39.13.10.1.1.4 Disulfides within Higher Ring Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 893

39.13.10.1.1.4.1 Method 1: Preparation from a Dibromide Using Disodium Disulfide . . . . . 89339.13.10.1.1.4.2 Method 2: Oxidation of a Dithiol Using Iron(III) Chloride . . . . . . . . . . . . . . . . 89439.13.10.1.1.4.3 Method 3: Preparation from a Bis(diazo) Compound Using Sulfur . . . . . . . 894

39.13.10.1.2 Cyclic Polysulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 895

39.13.10.1.2.1 1,2,3-Trithiolanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 895

39.13.10.1.2.1.1 Method 1: Sulfurization of a 1,2-Dithiol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89539.13.10.1.2.1.2 Method 2: Sulfurization of Tetrafluoroethene . . . . . . . . . . . . . . . . . . . . . . . . . . 89539.13.10.1.2.1.3 Method 3: Sulfurization of Norbornene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 896

39.13.10.1.2.2 1,2,3-Trithianes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 897

39.13.10.1.2.2.1 Method 1: Sulfurization of Sodium S,S¢-Propane-1,3-diyl Bis(thiosulfate) . 89739.13.10.1.2.2.2 Method 2: Sulfurization of Diphenylthiiranes . . . . . . . . . . . . . . . . . . . . . . . . . . 897

39.13.10.1.2.3 1,2,3-Trithiepane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 898

XLIV Table of Contents


39.13.10.1.2.3.1 Method 1: Sulfurization of a 3,6-Dihydro-1,2-dithiin . . . . . . . . . . . . . . . . . . . . 898

39.13.10.1.2.4 1,2,3,4-Tetrathiepane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 898

39.13.10.1.2.5 1,5-Dihydro-2,3,4-benzotrithiepanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 898

39.13.10.1.2.5.1 Method 1: Sulfurization of 1,2-Phenylenedimethanethiol . . . . . . . . . . . . . . . 898

39.13.10.1.2.6 Higher Cyclic Polysulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 899

39.13.10.1.2.6.1 Method 1: Sulfurization of Naphthalene-1,8-diyldimethanethiol . . . . . . . . 89939.13.10.1.2.6.2 Method 2: Sulfurization of Ethane-1,2-disulfenyl Dichloride . . . . . . . . . . . . . 900

39.14 Product Class 14: Alkaneselenonic Acids and Acyclic DerivativesJ. Drabowicz, P. Kiełbasinski, P. Łyzwa, and M. Mikołajczyk

39.14 Product Class 14: Alkaneselenonic Acids and Acyclic Derivatives . . . . . . . . . 903

39.14.1 Product Subclass 1: Alkaneselenonic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 904


39.14.1.1.1 Method 1: Oxidation of Alkaneseleninic Acids . . . . . . . . . . . . . . . . . . . . . . . . . 90439.14.1.1.2 Method 2: Oxidation of Diselenides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 905

39.14.2 Product Subclass 2: Alkaneselenonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 906


39.14.2.1.1 Method 1: Alkylation of the Silver Salts of Perfluoroalkaneselenonic Acids 906

39.14.3 Product Subclass 3: Alkaneselenonamides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 906


39.14.3.1.1 Method 1: Reaction of a Selenonate with an Amine . . . . . . . . . . . . . . . . . . . . 906

39.15 Product Class 15: Acyclic Dialkyl Selenones and DerivativesJ. Drabowicz, J. Lewkowski, W. Kudelska, and T. Girek

39.15 Product Class 15: Acyclic Dialkyl Selenones and Derivatives . . . . . . . . . . . . . . 909

39.15.1 Product Subclass 1: Dialkyltetrahalo-l6-selanes . . . . . . . . . . . . . . . . . . . . . . . . . . 909


39.15.1.1.1 Method 1: Reaction of Bis(trifluoromethyl)selenium Difluoride withElemental Fluorine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 910

39.15.2 Product Subclass 2: Dialkyl Selenones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 910


39.15.2.1.1 Method 1: Oxidation of Selenides or Selenoxides . . . . . . . . . . . . . . . . . . . . . . 91139.15.2.1.1.1 Variation 1: Oxidation with Peroxy Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . 91139.15.2.1.1.2 Variation 2: Oxidation with Sodium Hypochlorite . . . . . . . . . . . . . . . . . . . . . . . 91239.15.2.1.2 Method 2: Addition of Alkoxides to Methyl Styryl Selenone . . . . . . . . . . . . . 913

Table of Contents XLV


39.16 Product Class 16: Alkaneseleninic Acids and Acyclic DerivativesS. Braverman, M. Cherkinsky, and S. Levinger

39.16 Product Class 16: Alkaneseleninic Acids and Acyclic Derivatives . . . . . . . . . . 915

39.16.1 Product Subclass 1: Alkylselenium Trihalides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 915


39.16.1.1.1 Method 1: Synthesis from Diselenides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91539.16.1.1.2 Method 2: Synthesis from Seleninic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 915

39.16.2 Product Subclass 2: Alkaneseleninyl Chlorides . . . . . . . . . . . . . . . . . . . . . . . . . . . 916


39.16.2.1.1 Method 1: Oxidation of Selenenyl Chlorides . . . . . . . . . . . . . . . . . . . . . . . . . . . 91639.16.2.1.1.1 Variation 1: Ozonization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91639.16.2.1.1.2 Variation 2: Oxidation with Nitrogen Dioxide . . . . . . . . . . . . . . . . . . . . . . . . . . . 917

39.16.3 Product Subclass 3: Alkaneseleninic Acids and Their Salts . . . . . . . . . . . . . . . . 917


39.16.3.1.1 Method 1: Oxidation of Alkyl Selenocyanates . . . . . . . . . . . . . . . . . . . . . . . . . . 91839.16.3.1.2 Method 2: Hydrolysis of Alkylselenium Trihalides . . . . . . . . . . . . . . . . . . . . . . 91939.16.3.1.3 Method 3: Hydrolysis of Seleninic Anhydrides . . . . . . . . . . . . . . . . . . . . . . . . . . 91939.16.3.1.4 Method 4: Hydrolysis of Selenoseleninates . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91939.16.3.1.5 Method 5: Oxidative Cleavage of Dialkyl Diselenides . . . . . . . . . . . . . . . . . . . 92039.16.3.1.5.1 Variation 1: Oxidation with Nitric Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92139.16.3.1.5.2 Variation 2: Oxidation with Hydrogen Peroxide . . . . . . . . . . . . . . . . . . . . . . . . . 92139.16.3.1.6 Method 6: Oxidation of Alkaneselenenic Acids . . . . . . . . . . . . . . . . . . . . . . . . . 922


39.16.3.2.1 Method 1: Catalytic Oxidation with Perfluorooctaneseleninic Acid . . . . . . 923

39.16.4 Product Subclass 4: Alkaneseleninic Acid Esters (Seleninates) . . . . . . . . . . . . 924


39.16.4.1.1 Method 1: Alkylation of Seleninate Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92439.16.4.1.2 Method 2: Alcoholysis of Alkaneseleninyl Chlorides or Anhydrides . . . . . . 925

39.16.5 Product Subclass 5: Alkaneseleninic Anhydrides . . . . . . . . . . . . . . . . . . . . . . . . . 925


39.16.5.1.1 Method 1: Oxidation of Diselenides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92539.16.5.1.1.1 Variation 1: Ozonization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92639.16.5.1.1.2 Variation 2: With tert-Butyl Hydroperoxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 926

39.17 Product Class 17: Acyclic Dialkyl Selenoxides and DerivativesT. Shimizu and N. Kamigata

39.17 Product Class 17: Acyclic Dialkyl Selenoxides and Derivatives . . . . . . . . . . . . 929

39.17.1 Product Subclass 1: Acyclic Dialkylselenium Dihalides . . . . . . . . . . . . . . . . . . . 929


39.17.1.1.1 Method 1: Halogenation of Selenides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 930

XLVI Table of Contents


39.17.1.1.1.1 Variation 1: With Molecular Halogens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93039.17.1.1.1.2 Variation 2: With Phosphorus Pentachloride or Silver(II) Fluoride . . . . . . . . . 93139.17.1.1.2 Method 2: Addition of Selenium Tetrahalides to Alkenes . . . . . . . . . . . . . . . 93139.17.1.1.3 Method 3: Reaction of Ketones with Selenium Oxychloride . . . . . . . . . . . . . 93239.17.1.1.4 Method 4: Reaction of Phenacyl Bromides with Selenium Powder . . . . . . . 93339.17.1.1.5 Methods 5: Miscellaneous Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 933

39.17.2 Product Subclass 2: Acyclic Dialkyl Selenoxides . . . . . . . . . . . . . . . . . . . . . . . . . . 934


39.17.2.1.1 Method 1: Oxidation of Dialkyl Selenides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93539.17.2.1.1.1 Variation 1: Using Hydrogen Peroxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93539.17.2.1.1.2 Variation 2: Using 3-Chloroperoxybenzoic Acid . . . . . . . . . . . . . . . . . . . . . . . . . 93539.17.2.1.1.3 Variation 3: Using Sodium Periodate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93639.17.2.1.1.4 Variation 4: Using Ozone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93639.17.2.1.2 Method 2: Synthesis from Dialkylselenium Dihalides . . . . . . . . . . . . . . . . . . . 93739.17.2.1.2.1 Variation 1: Hydrolysis of Dialkylselenium Dihalides . . . . . . . . . . . . . . . . . . . . . 93739.17.2.1.2.2 Variation 2: Dehalogenation Oxidation of Dialkylselenium Dibromides

with Silver(I) Oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 938

39.18 Product Class 18: AlkaneselenolsJ. V. Comasseto and A. S. Guarezemini

39.18 Product Class 18: Alkaneselenols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 941

39.18.1 Synthesis of Product Class 18 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 941

39.18.1.1 Method 1: Reaction of Alkylating Agents with Alkali Metal Selenides . . . . 94139.18.1.2 Method 2: Reaction of Selenourea with Alkyl Halides Followed by

Hydrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94239.18.1.3 Method 3: Reduction of Dialkyl Diselenides and Alkyl Selenocyanates . . . 94239.18.1.3.1 Variation 1: With Hypophosphorous Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94339.18.1.3.2 Variation 2: With Sodium in Liquid Ammonia Followed by Acidification . . . 94439.18.1.3.3 Variation 3: With Sodium Borohydride or Lithium Aluminum Hydride

Followed by Acidification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94439.18.1.4 Method 4: Reaction of Elemental Selenium with Alkyl Grignard or

Alkyllithium Compounds Followed by Hydrolysis . . . . . . . . . . . . 945

39.19 Product Class 19: Acyclic Alkaneselenolates

39.19.1 Product Subclass 1: Alkaneselenolates of Group 1, 2, and 13–15 MetalsJ. V. Comasseto and A. S. Guarezemini

39.19.1 Product Subclass 1: Alkaneselenolates of Group 1, 2, and 13–15 Metals . . 947


39.19.1.1.1 Arsenic Alkaneselenolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 947

39.19.1.1.1.1 Method 1: Reaction of Alkaneselenols or Sodium Alkaneselenolates withAmino- or Haloarsines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 947

39.19.1.1.1.2 Method 2: Reaction of Trimethyl(methylselanyl)silane with Haloarsines . 948

Table of Contents XLVII


39.19.1.1.2 Silicon Alkaneselenolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 948

39.19.1.1.2.1 Method 1: Reaction of Metal Alkaneselenolates with Halosilanes . . . . . . . 94939.19.1.1.2.2 Method 2: Alkylation of Sodium Trimethylsilaneselenolate . . . . . . . . . . . . . 949

39.19.1.1.3 Germanium Alkaneselenolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 950

39.19.1.1.3.1 Method 1: Reaction of Lithium Ethaneselenolate with Chlorotrimethyl-germane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 950

39.19.1.1.4 Tin Alkaneselenolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 950

39.19.1.1.4.1 Method 1: Reaction of Lithium Ethaneselenolate with Chlorotrimethyl-stannane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 950

39.19.1.1.4.2 Method 2: Reaction of Dialkyl Diselenides with Hydrazine HydrateFollowed by Chlorotriethylstannane . . . . . . . . . . . . . . . . . . . . . . . . 951

39.19.1.1.5 Lead Alkaneselenolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 951

39.19.1.1.5.1 Method 1: Reaction of Lithium Methaneselenolate with Chlorotrimethyl-plumbane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 951

39.19.1.1.6 Boron Alkaneselenolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 952

39.19.1.1.7 Aluminum Alkaneselenolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 952

39.19.1.1.8 Gallium Alkaneselenolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 952

39.19.1.1.8.1 Method 1: Reaction of Ethaneselenol with Bromodiisopropylgallium(III) . 95239.19.1.1.8.2 Method 2: Reaction of Ethaneselenol with Diiodo(methylsulfanyl)galli-

um(III) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 953

39.19.1.1.9 Indium Alkaneselenolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 953

39.19.1.1.9.1 Method 1: Reaction of Ethaneselenol with Diiodo(isopropyl)indium(III) . . 95339.19.1.1.9.2 Method 2: Reaction of Dialkyl Diselenides with Indium(I) Iodide . . . . . . . . 953

39.19.1.1.10 Magnesium Alkaneselenolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 954

39.19.1.1.10.1 Method 1: Insertion of Elemental Selenium into C—Mg Bonds . . . . . . . . . . 954

39.19.1.1.11 Lithium Alkaneselenolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 954

39.19.1.1.11.1 Method 1: Insertion of Elemental Selenium into C—Li Bonds . . . . . . . . . . . . 95439.19.1.1.11.1.1 Variation 1: Reaction of Alkyllithiums and Elemental Selenium . . . . . . . . . . . 95439.19.1.1.11.1.2 Variation 2: Reaction of Lithium Enolates and Elemental Selenium . . . . . . . 95539.19.1.1.11.1.3 Variation 3: Reaction of Alkyl Selenocyanates with Lithium Hydrides . . . . . 956

39.19.1.1.12 Sodium Alkaneselenolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 956

39.19.1.1.12.1 Method 1: Deprotonation of Alkaneselenols . . . . . . . . . . . . . . . . . . . . . . . . . . . 95639.19.1.1.12.2 Method 2: Reduction of Dialkyl Diselenides . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95739.19.1.1.12.2.1 Variation 1: With Metallic Sodium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95739.19.1.1.12.2.2 Variation 2: With Sodium Borohydride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95739.19.1.1.12.2.3 Variation 3: With Sodium Hydride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 957

39.19.1.1.13 Potassium Alkaneselenolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 957

39.19.1.1.13.1 Method 1: Deprotonation of Alkaneselenols . . . . . . . . . . . . . . . . . . . . . . . . . . . 95739.19.1.1.13.2 Method 2: Reaction of Dialkyl Diselenides and Alkyl Selenocyanates

with Potassium Hydride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 958

XLVIII Table of Contents


39.19.2 Product Subclass 2: Alkaneselenolates of Group 3–12 MetalsA. Polo and J. Real

39.19.2 Product Subclass 2: Alkaneselenolates of Group 3–12 Metals . . . . . . . . . . . . 961


39.19.2.1.1 Terminal Alkaneselenolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 961

39.19.2.1.1.1 Method 1: Reaction of a Metal Complex with a Main GroupAlkaneselenolate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 961

39.19.2.1.1.2 Method 2: Alkylation of Coordinated Selenides with Alkyl Halides . . . . . . . 96339.19.2.1.1.3 Method 3: Alkylation of a Hydroselenide Ligand . . . . . . . . . . . . . . . . . . . . . . . 96339.19.2.1.1.4 Method 4: Reaction of a Dialkyl Diselenide with a Metal Complex . . . . . . . 96439.19.2.1.1.4.1 Variation 1: By Hydride/Selenolate Ligand Exchange . . . . . . . . . . . . . . . . . . . . . 96439.19.2.1.1.4.2 Variation 2: By Oxidative Addition to a Metal Center . . . . . . . . . . . . . . . . . . . . 96539.19.2.1.1.5 Method 5: Insertion of Elemental Selenium into the Transition

Metal—Alkyl Bond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96739.19.2.1.1.6 Methods 6: Miscellaneous Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 967

39.19.2.1.2 m2-Alkaneselenolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 968

39.19.2.1.2.1 Method 1: Reaction of a Metal Complex with a Main GroupAlkaneselenolate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 968

39.19.2.1.2.1.1 Variation 1: From Metal Halide Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96839.19.2.1.2.1.2 Variation 2: From Metal Carbonyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . 96839.19.2.1.2.2 Method 2: Reaction of Bridging Coordinated Selenides with Electrophiles

and Nucleophiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96939.19.2.1.2.3 Method 3: Reaction of a Metal Salt with an Alkyl Trimethylsilyl Selenide . 97139.19.2.1.2.4 Method 4: Oxidative Addition of a Dialkyl Diselenide or

(Alkylselanyl)phosphine to a Metal Complex . . . . . . . . . . . . . . . . 97139.19.2.1.2.5 Method 5: Reaction of a Selenolate–Metal Complex with a Second Metal

Complex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97239.19.2.1.2.6 Methods 6: Miscellaneous Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 973

39.19.2.1.3 m3-Alkaneselenolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 973

39.19.2.1.3.1 Method 1: Reaction of a Metal Salt with an Alkyl Trimethylsilyl Selenide . 973


39.19.2.2.1 Method 1: Propargylic Substitution Reactions Catalyzed bym2-Alkaneselenolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 973

39.20 Product Class 20: Acyclic Dialkyl SelenidesM. Segi

39.20 Product Class 20: Acyclic Dialkyl Selenides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 977

39.20.1 Synthesis of Product Class 20 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 977

39.20.1.1 Method 1: Synthesis from Alkaneselenols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97739.20.1.1.1 Variation 1: By Reaction with Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97739.20.1.1.2 Variation 2: By Substitution with Alkyl Halides via Selenolates . . . . . . . . . . 97839.20.1.2 Method 2: Synthesis from Selenolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 979

Table of Contents XLIX


39.20.1.2.1 Variation 1: Unsymmetrical Selenides by Addition to Alkenes . . . . . . . . . . . 97939.20.1.2.2 Variation 2: Symmetrical Selenides by Substitution with Alkyl Halides . . . 97939.20.1.2.3 Variation 3: Unsymmetrical Selenides by the Substitution of

Alkaneselenolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98139.20.1.2.4 Variation 4: By Substitution with Sulfonates, Sulfonium Salts, or

Ammonium Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98239.20.1.2.5 Variation 5: By Reaction with Lactones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98339.20.1.2.6 Variation 6: By Reaction with Epoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98439.20.1.2.7 Variation 7: By Reaction with 4,5-Dihydrooxazoles . . . . . . . . . . . . . . . . . . . . . 98439.20.1.3 Method 3: Synthesis from Alkaneselenenyl Halides and Other

Selanylating Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98539.20.1.4 Method 4: Synthesis from Acyclic Diselenides . . . . . . . . . . . . . . . . . . . . . . . . . 98639.20.1.4.1 Variation 1: By Additions to Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98639.20.1.4.2 Variation 2: By Reactions with Carbon Radicals . . . . . . . . . . . . . . . . . . . . . . . . . 98739.20.1.5 Method 5: Synthesis from Se,Se-Acetals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98839.20.1.6 Method 6: Synthesis from Acyclic Selenoxides . . . . . . . . . . . . . . . . . . . . . . . . 98939.20.1.7 Method 7: Synthesis from Selenonium Ylides . . . . . . . . . . . . . . . . . . . . . . . . . 99039.20.1.8 Methods 8: Miscellaneous Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 991

39.20.2 Applications of Product Class 20 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . . . 991

39.20.2.1 Method 1: Asymmetric Syntheses Using Chiral Dialkyl Selenides asCatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 991

39.21 Product Class 21: Acyclic Trialkylselenonium Salts and DerivativesY. Tang and X.-L. Sun

39.21 Product Class 21: Acyclic Trialkylselenonium Salts and Derivatives . . . . . . 995

39.21.1 Synthesis of Product Class 21 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 996

39.21.1.1 Method 1: Reaction of Selenides with Alkylating Agents . . . . . . . . . . . . . . . 99639.21.1.2 Method 2: Ring-Opening Reaction of Selenetane Derivatives with Alkyl

Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99839.21.1.3 Method 3: Reaction of Dialkyl Diselenides with Alkyl Halides . . . . . . . . . . 99939.21.1.4 Method 4: Reaction of Selenium with Alkyl Halides . . . . . . . . . . . . . . . . . . . 100039.21.1.5 Method 5: Reaction of Alkoxy(chloro)-l4-selenolanes with Grignard

Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100139.21.1.6 Method 6: Anion Exchange of Selenonium Salts . . . . . . . . . . . . . . . . . . . . . . . 1001

39.22 Product Class 22: Alkaneselenenic Acids and Acyclic DerivativesT. Wirth

39.22 Product Class 22: Alkaneselenenic Acids and Acyclic Derivatives . . . . . . . . 1005

39.22.1 Product Subclass 1: Alkaneselenenyl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1005


39.22.1.1.1 Method 1: Synthesis Using Elemental Bromine . . . . . . . . . . . . . . . . . . . . . . . . 100539.22.1.1.2 Method 2: Synthesis Using Sulfuryl Chloride . . . . . . . . . . . . . . . . . . . . . . . . . . 1006

L Table of Contents


39.22.2 Product Subclass 2: Alkaneselenenic Acids and Esters . . . . . . . . . . . . . . . . . . . 1006


39.22.3 Product Subclass 3: Alkaneselenenamides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1007


39.22.4 Product Subclass 4: (Alkylselanyl)phosphines . . . . . . . . . . . . . . . . . . . . . . . . . . . 1008


39.22.4.1.1 Method 1: Synthesis from Diselenides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100839.22.4.1.1.1 Variation 1: Reaction of Dialkyl Diselenides with Tetraorganodiphos-

phines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100839.22.4.1.1.2 Variation 2: Reaction of Dialkyl Diselenides with Diphosphine Dioxides

and Diphosphine Disulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100939.22.4.1.2 Method 2: Synthesis with Phosphorus Halides . . . . . . . . . . . . . . . . . . . . . . . . 100939.22.4.1.2.1 Variation 1: Reaction of Organometallic Reagents with

Phosphinoselenoic Chlorides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100939.22.4.1.2.2 Variation 2: Reaction of Methyl Trimethylsilyl Selenide with

Chlorophosphines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101039.22.4.1.3 Method 3: Alkylation of S-Alkyl Phosphinoselenothioates and

(Selenoxo)phosphines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1011

39.23 Product Class 23: Acyclic Di- and PolyselenidesR. Sato and T. Kimura

39.23 Product Class 23: Acyclic Di- and Polyselenides . . . . . . . . . . . . . . . . . . . . . . . . . 1013

39.23.1 Product Subclass 1: Monoalkyl Diselenides and Polyselenides and TheirMetal Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1013

39.23.2 Product Subclass 2: Symmetrical Dialkyl Diselenides . . . . . . . . . . . . . . . . . . . . 1013


39.23.2.1.1 Method 1: Reaction of Alkyl Halides with Metal Diselenides . . . . . . . . . . . 101439.23.2.1.1.1 Variation 1: Reaction with Dilithium Diselenide . . . . . . . . . . . . . . . . . . . . . . . . 101439.23.2.1.1.2 Variation 2: Reaction with Bis(methoxymagnesium) Diselenide . . . . . . . . . 101539.23.2.1.1.3 Variation 3: Reaction with Disodium Diselenide . . . . . . . . . . . . . . . . . . . . . . . . 101639.23.2.1.2 Method 2: Reaction of Selenium with Organolithium Reagents

Followed by Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101639.23.2.1.3 Method 3: Oxidation of Selenols or Metal Selenolates . . . . . . . . . . . . . . . . . 101739.23.2.1.4 Method 4: Hydrolysis of Selenocyanates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101839.23.2.1.5 Method 5: Synthesis from Se-Alkyl Selenosulfates . . . . . . . . . . . . . . . . . . . . . 101839.23.2.1.5.1 Variation 1: Hydrolysis of Selenosulfates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101839.23.2.1.5.2 Variation 2: Pyrolysis of (2-Aminoethyl)selenosulfuric Acid . . . . . . . . . . . . . . 101939.23.2.1.6 Method 6: Reduction of a Selenenic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1020

39.23.3 Product Subclass 3: Symmetrical Dialkyl Polyselenides . . . . . . . . . . . . . . . . . 1021


39.23.3.1.1 Method 1: Synthesis from an Alkyl Halide and Selenium . . . . . . . . . . . . . . . 1021

Table of Contents LI


39.24 Product Class 24: Seleniranes and DerivativesM. Saito and J. Nakayama

39.24 Product Class 24: Seleniranes and Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . 1023

39.24.1 Product Subclass 1: Seleniranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1023


39.24.1.2 Applications of Product Subclass 1 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 1024

39.24.1.2.1 Method 1: Alkene Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102439.24.1.2.2 Method 2: Seleniranes as Selenation Reagents . . . . . . . . . . . . . . . . . . . . . . . . 1026

39.24.2 Product Subclass 2: Seleniranium Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1026



39.24.2.2.1 Method 1: Asymmetric Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102839.24.2.2.2 Method 2: Heterocycle Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1030

39.25 Product Class 25: Selenetanes and DerivativesE. Block

39.25 Product Class 25: Selenetanes and Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . 1033

39.25.1 Product Subclass 1: Selenetanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1033


39.25.1.1.1 Synthesis by Ring-Closure Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1033

39.25.1.1.1.1 Method 1: Synthesis from 1,3-Dihalides or Related Compounds withSelenide Ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1033

39.25.1.1.1.2 Method 2: Synthesis from 2-Substituted 2-(Chloromethyl)oxiranes andSelenide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1035

39.25.1.1.1.3 Method 3: Synthesis from Norbornadiene and Selenium Tetrabromide . 103639.25.1.1.1.4 Method 4: Cycloaddition of Selenocarbonyl Compounds and Alkenes . . 103639.25.1.1.1.5 Method 5: Synthesis from 2-[(3-Hydroxyalkyl)selanyl]benzoxazoles . . . . 1037

39.25.1.1.2 Synthesis by Ring Transformation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1037

39.25.1.1.2.1 Method 1: Ring Transformations of 3-Halomethyl-2,3-dihydro-selenazolium Salts with Base . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1037

39.25.1.1.2.2 Method 2: Ring Transformations of 1,3,4-Oxadiselenolanes withTrivalent Phosphorus Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1038

39.25.1.1.3 Synthesis by Substituent Modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1038

39.25.1.1.3.1 Method 1: Esterification and Other Reactions of Selenetan-3-ols . . . . . . . 103839.25.1.1.3.2 Method 2: Cleavage of a Spirocyclic Ring Bond . . . . . . . . . . . . . . . . . . . . . . . 103939.25.1.1.3.3 Method 3: l4-Selenane Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1039

39.25.2 Product Subclass 2: 1,2-Oxaselenetanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1040


39.25.2.1.1 Synthesis by Ring-Closure Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1040

39.25.2.1.1.1 Method 1: Synthesis by Treatment with Bromine . . . . . . . . . . . . . . . . . . . . . 1040

LII Table of Contents


39.26 Product Class 26: Selenolanes, Larger Rings, and Derivativesof Various Oxidation StatesR. Sato and T. Kimura

39.26 Product Class 26: Selenolanes, Larger Rings, and Derivativesof Various Oxidation States . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1043

39.26.1 Product Subclass 1: Cyclic Alkaneselenonic Acid DerivativesR. Sato and T. Kimura

39.26.1 Product Subclass 1: Cyclic Alkaneselenonic Acid Derivatives . . . . . . . . . . . . 1045

39.26.2 Product Subclass 2: Cyclic Dialkyl Selenones and DerivativesR. Sato and T. Kimura

39.26.2 Product Subclass 2: Cyclic Dialkyl Selenones and Derivatives . . . . . . . . . . . . 1047

39.26.3 Product Subclass 3: Cyclic Alkaneseleninic Acid DerivativesR. Sato and T. Kimura

39.26.3 Product Subclass 3: Cyclic Alkaneseleninic Acid Derivatives . . . . . . . . . . . . . 1049


39.26.3.1.1 Cyclic Seleninic Acid Esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1049

39.26.3.1.1.1 Method 1: Diels–Alder Reaction of Selenium Dioxide with 1,3-Dienes . . 104939.26.3.1.1.2 Method 2: Oxidation of 3,3-Dimethylselenetane with Hydrogen

Peroxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104939.26.3.1.1.3 Method 3: Oxidation with tert-Butyl Hydroperoxide . . . . . . . . . . . . . . . . . . . 1050

39.26.4 Product Subclass 4: Cyclic Dialkyl Selenoxides and DerivativesT. Shimizu and N. Kamigata

39.26.4 Product Subclass 4: Cyclic Dialkyl Selenoxides and Derivatives . . . . . . . . . . 1053


39.26.4.1.1 Cyclic Dihalo-l4-selanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1053

39.26.4.1.1.1 Method 1: Halogenation of Cyclic Selenides . . . . . . . . . . . . . . . . . . . . . . . . . . 105339.26.4.1.1.2 Method 2: Oxidative Cyclization of Aldehydes with Selenium Dioxide . . 1054

39.26.4.1.2 Cyclic Selenoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1054

39.26.4.1.2.1 Method 1: Oxidation of Selenides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105439.26.4.1.2.2 Methods 2: Other Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1056

39.26.4.1.3 Cyclic Selenimides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1056

39.26.4.1.3.1 Method 1: Imidation of Cyclic Selenides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1056

Table of Contents LIII


39.26.5 Product Subclass 5: Cyclic Alkaneselenolates of Group 1, 2, and 13–15MetalsN. Kambe

39.26.5 Product Subclass 5: Cyclic Alkaneselenolates of Group 1, 2, and 13–15Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1059


39.26.5.1.1 Method 1: Chelation of Selenides to Metal Halides . . . . . . . . . . . . . . . . . . . . 105939.26.5.1.2 Method 2: Dimerization of Metal Selenolates . . . . . . . . . . . . . . . . . . . . . . . . . 105939.26.5.1.3 Method 3: Cycloaddition of Selenoxometal Compounds with

Buta-1,3-dienes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106039.26.5.1.4 Method 4: Reaction of Elemental Selenium with Metallacycles . . . . . . . . . 1060

39.26.6 Product Subclass 6: Cyclic Alkaneselenolates of Group 3–12 MetalsA. Polo and J. Real

39.26.6 Product Subclass 6: Cyclic Alkaneselenolates of Group 3–12 Metals . . . . . 1063


39.26.6.1.1 Method 1: Synthesis of Cyclic Diselenolates . . . . . . . . . . . . . . . . . . . . . . . . . . 106339.26.6.1.1.1 Variation 1: Alkylation of Bridging Coordinated Selenides with

Dihaloalkanes or Diazomethane . . . . . . . . . . . . . . . . . . . . . . . . . . . 106339.26.6.1.1.2 Variation 2: Substitution of a Metal Halide with a Main Group

Alkanediselenolate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106539.26.6.1.2 Method 2: Synthesis of Cyclic Selenolates with a Metal—Carbon Bond . . 106639.26.6.1.2.1 Variation 1: Cyclic Alkenylalkaneselenolates by Se-Dealkylation . . . . . . . . . 106639.26.6.1.2.2 Variation 2: Synthesis of Selenoformaldehyde Complexes . . . . . . . . . . . . . . 106639.26.6.1.3 Method 3: Synthesis of Cyclic Aminoselenolates by Reaction of Sodium

Aminoalkaneselenolates with a Metal Halide Complex . . . . . . 1067

39.26.7 Product Subclass 7: Cyclic Dialkyl SelenidesM. Segi

39.26.7 Product Subclass 7: Cyclic Dialkyl Selenides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1069


39.26.7.1.1 Method 1: Synthesis from Metal Selenides . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106939.26.7.1.1.1 Variation 1: By Substitution with Dihalides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106939.26.7.1.1.2 Variation 2: By Substitution with Dimethanesulfonates . . . . . . . . . . . . . . . . . 107139.26.7.1.1.3 Variation 3: By Substitution with Cyclic Ammonium Salts . . . . . . . . . . . . . . . 107139.26.7.1.1.4 Variation 4: By Addition to Enones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107239.26.7.1.1.5 Variation 5: By Reaction with Diepoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107239.26.7.1.2 Method 2: Synthesis from Alkyl Selenocyanates . . . . . . . . . . . . . . . . . . . . . . . 107339.26.7.1.3 Method 3: Synthesis from Benzyl Selenides via Radical Cyclizations . . . . 107439.26.7.1.4 Method 4: Synthesis from Mixed O,Se-Acetals . . . . . . . . . . . . . . . . . . . . . . . . 107639.26.7.1.5 Method 5: Synthesis from Selenacycles by the Rearrangement of

Selenonium Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107639.26.7.1.6 Method 6: Synthesis from Selenocarbonyl Compounds . . . . . . . . . . . . . . . . 1077

LIV Table of Contents


39.26.7.1.6.1 Variation 1: By Cycloaddition of Selenoaldehydes . . . . . . . . . . . . . . . . . . . . . . 107739.26.7.1.6.2 Variation 2: By Cycloaddition of Selenoketones . . . . . . . . . . . . . . . . . . . . . . . . 107839.26.7.1.7 Methods 7: Miscellaneous Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1079


39.26.7.2.1 Method 1: Asymmetric Conversion of Aldehydes into EpoxidesUsing Chiral Cyclic Selenides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1080

39.26.8 Product Subclass 8: Cyclic Trialkylselenonium Salts and DerivativesY. Tang and X.-L. Sun

39.26.8 Product Subclass 8: Cyclic Trialkylselenonium Salts and Derivatives . . . . . 1083


39.26.8.1.1 Method 1: Reaction of Cyclic Selenides with Alkylating Agents . . . . . . . . . 108439.26.8.1.2 Method 2: Reaction of Cyclic Dialkyl(halo)selenonium Salts . . . . . . . . . . . . 108839.26.8.1.3 Method 3: Reaction of Cyclic Selenonium Ylides . . . . . . . . . . . . . . . . . . . . . . 108939.26.8.1.4 Method 4: Anion Exchange of Cyclic Selenonium Salts . . . . . . . . . . . . . . . . 1089

39.26.9 Product Subclass 9: Cyclic Alkaneselenenic Acid DerivativesT. Wirth


39.26.9.1.1 Method 1: Synthesis of Alkaneselenenic Acid Derivatives with a Se—NBond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1093

39.26.9.1.2 Method 2: Synthesis of Alkaneselenenic Acid Derivatives with a Se—PBond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1094

39.26.10 Product Subclass 10: Cyclic Dialkyl Di- and PolyselenidesR. Sato and T. Kimura

39.26.10 Product Subclass 10: Cyclic Dialkyl Di- and Polyselenides . . . . . . . . . . . . . . . 1097

39.26.10.1 Synthesis of Product Subclass 10 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1097

39.26.10.1.1 Cyclic Dialkyl Diselenides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1097

39.26.10.1.1.1 1,2-Diselenolanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1097

39.26.10.1.1.1.1 Method 1: Synthesis from Selenocyanates . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109739.26.10.1.1.1.1.1 Variation 1: Alkaline Hydrolysis of Bis(selenocyanates) with Sodium

Ethoxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109839.26.10.1.1.1.1.2 Variation 2: Pyrolysis of Bis(selenocyanates) . . . . . . . . . . . . . . . . . . . . . . . . . . . 109939.26.10.1.1.1.1.3 Variation 3: Acid Hydrolysis of Bis(selenocyanates) . . . . . . . . . . . . . . . . . . . . . 109939.26.10.1.1.1.2 Method 2: Synthesis from Dihaloalkanes and Disodium Diselenide . . . . . 110039.26.10.1.1.1.3 Method 3: Synthesis via Birch Reduction of Dibenzyl Selenides . . . . . . . . 110139.26.10.1.1.1.4 Method 4: Synthesis by Selenation of Quinazolinones . . . . . . . . . . . . . . . . . 1102

39.26.10.1.1.2 1,2-Diselenanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1102

39.26.10.1.1.2.1 Method 1: Synthesis from Diepoxides and Disodium Diselenide . . . . . . . 1102

39.26.10.1.1.3 1,4-Dihydro-2,3-benzodiselenin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1103

Table of Contents LV


39.26.10.1.1.4 Diselenides with Higher Ring Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1103

39.26.10.1.1.4.1 Method 1: Synthesis from Bis(diazo) Compounds. . . . . . . . . . . . . . . . . . . . . 110339.26.10.1.1.4.2 Method 2: Synthesis of Cyclophanes by Hydrolysis of Bis(selenocya-

nates) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1104

39.26.10.1.2 Cyclic Dialkyl Polyselenides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1106

39.26.10.1.2.1 Method 1: Hydrolysis of Selenocyanates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1106

39.27 Product Class 27: Alkanetelluronic Acids and Acyclic DerivativesJ. Drabowicz, P. Kiełbasinski, P. Łyzwa, and M. Mikołajczyk

39.27 Product Class 27: Alkanetelluronic Acids and Acyclic Derivatives . . . . . . . . 1109

39.28 Product Class 28: Acyclic Dialkyl Tellurones and DerivativesJ. Drabowicz, J. Lewkowski, W. Kudelska, and T. Girek

39.28 Product Class 28: Acyclic Dialkyl Tellurones and Derivatives . . . . . . . . . . . . 1111

39.28.1 Product Subclass 1: Dialkyltetrahalo-l6-tellanes . . . . . . . . . . . . . . . . . . . . . . . . 1111


39.28.1.1.1 Method 1: Halogenation of Dialkyl Tellurides or Dialkyldihalo-l4-tellanes 1112

39.28.2 Product Subclass 2: Dialkyl Tellurones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1113


39.28.2.1.1 Method 1: Oxidation of Tellurides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111339.28.2.1.1.1 Variation 1: Oxidation with Peroxo Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . 111339.28.2.1.1.2 Variation 2: Oxidation with Sodium Hypochlorite . . . . . . . . . . . . . . . . . . . . . . 1114

39.28.3 Product Subclass 3: Higher Alkylated Tellurium(VI) Derivatives . . . . . . . . . 1114


39.28.3.1.1 Method 1: Preparation of cis-Tetramethyltellurium Difluoride andHexamethyl-l6-tellane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1114

39.29 Product Class 29: Alkanetellurinic Acids and Acyclic DerivativesS. Braverman, M. Cherkinsky, and S. Levinger

39.29 Product Class 29: Alkanetellurinic Acids and Acyclic Derivatives . . . . . . . . 1117

39.29.1 Product Subclass 1: Alkyltellurium Trihalides . . . . . . . . . . . . . . . . . . . . . . . . . . . 1117


39.29.1.1.1 Method 1: Exchange Reactions of Tellurium Tetrahalides withOrganometallic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1117

39.29.1.1.2 Method 2: Halogenolysis of Dialkyl Ditellurides . . . . . . . . . . . . . . . . . . . . . . . 111739.29.1.1.3 Method 3: Halogenolysis of Dialkyl Tellurides . . . . . . . . . . . . . . . . . . . . . . . . . 111839.29.1.1.4 Method 4: Halogenolysis of Tellurocyanates . . . . . . . . . . . . . . . . . . . . . . . . . . 111939.29.1.1.5 Method 5: Telluration of Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112039.29.1.1.5.1 Variation 1: Addition of a Tellurium Tetrahalide . . . . . . . . . . . . . . . . . . . . . . . . 112039.29.1.1.5.2 Variation 2: Alkoxytelluration in the Presence of an Alcohol . . . . . . . . . . . . . 1121

LVI Table of Contents


39.29.1.1.5.3 Variation 3: Chlorotelluration in a 1,3-syn Mode via Acyloxy Migration . . . 112139.29.1.1.5.4 Variation 4: Addition of a Tellurium Tetrahalide Generated In Situ from

Tellurium Dioxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112239.29.1.1.6 Method 6: Halogen Exchange of Alkyltellurium Trihalides . . . . . . . . . . . . . . 1122

39.29.2 Product Subclass 2: Alkyltellurium Triazides . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1123


39.29.2.1.1 Method 1: Substitution of Alkyltellurium Trifluorides with Azide . . . . . . . 1123

39.29.3 Product Subclass 3: Alkanetellurinic Acids and Salts . . . . . . . . . . . . . . . . . . . . 1124


39.29.3.1.1 Method 1: Hydrolysis of Alkyltellurium Trihalides . . . . . . . . . . . . . . . . . . . . . 112439.29.3.1.2 Method 2: Oxidation of Dialkyl Tellurides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1124

39.30 Product Class 30: Acyclic Dialkyl Telluroxides and DerivativesT. Shimizu and N. Kamigata

39.30 Product Class 30: Acyclic Dialkyl Telluroxides and Derivatives . . . . . . . . . . . 1127

39.30.1 Product Subclass 1: Acyclic Dialkyltellurium Dihydroxides . . . . . . . . . . . . . . 1127


39.30.1.1.1 Method 1: Oxidation of Tellurides with N-Chlorosuccinimide . . . . . . . . . . . 1127

39.30.2 Product Subclass 2: Acyclic Dialkyltellurium Dihalides . . . . . . . . . . . . . . . . . . 1128


39.30.2.1.1 Method 1: Halogenation of Tellurides with Molecular Halogens . . . . . . . . 112839.30.2.1.2 Method 2: Chlorination of Tellurides with Thionyl Chloride . . . . . . . . . . . . 113039.30.2.1.3 Method 3: Chlorination of Tellurides with Sulfuryl Chloride . . . . . . . . . . . . 113039.30.2.1.4 Method 4: Fluorination of Tellurides with Xenon Difluoride and Sulfuryl

Chloride Fluoride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113139.30.2.1.5 Method 5: Synthesis from Tellurium Tetrahalides . . . . . . . . . . . . . . . . . . . . . 113239.30.2.1.6 Method 6: Reaction of a-Halo Ketones with Tellurium Powder . . . . . . . . . 113339.30.2.1.7 Methods 7: Other Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1134

39.30.3 Product Subclass 3: Other Derivatives of Acyclic Dialkyl Telluroxides . . . . 1134


39.30.3.1.1 Methods 1: Miscellaneous Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1134

39.31 Product Class 31: AlkanetellurolsJ. V. Comasseto and A. S. Guarezemini

39.31 Product Class 31: Alkanetellurols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1137


39.31.1.1 Method 1: Protonation of Alkali Metal Alkanetellurolates . . . . . . . . . . . . . . 113739.31.1.2 Method 2: Methanolysis of Trimethylsilyl Alkanetellurolates . . . . . . . . . . . 1138

Table of Contents LVII


39.32 Product Class 32: Acyclic Alkanetellurolates

39.32.1 Product Subclass 1: Alkanetellurolates of Group 1, 2, and 13–15 MetalsJ. V. Comasseto and A. S. Guarezemini

39.32.1 Product Subclass 1: Alkanetellurolates of Group 1, 2, and 13–15 Metals . 1139


39.32.1.1.1 Arsenic Alkanetellurolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1139

39.32.1.1.1.1 Method 1: Reaction of Tetraalkyldiarsines with Dialkyl Ditellurides . . . . . 1139

39.32.1.1.2 Antimony Alkanetellurolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1139

39.32.1.1.2.1 Method 1: Reaction of Lithium Alkanetellurolates withDialkylbromostibine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1139

39.32.1.1.3 Silicon Alkanetellurolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1139

39.32.1.1.3.1 Method 1: Reaction of Lithium Alkanetellurolates with Silyl Halides . . . . 1139

39.32.1.1.4 Germanium Alkanetellurolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1140

39.32.1.1.5 Tin Alkanetellurolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1140

39.32.1.1.6 Aluminum Alkanetellurolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1140

39.32.1.1.6.1 Method 1: Reaction of Dibutyl Ditelluride with DiisobutylaluminumHydride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1140

39.32.1.1.6.2 Method 2: Reaction of Trimethylaluminum with Elemental Tellurium . . . 1141

39.32.1.1.7 Gallium Alkanetellurolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1141

39.32.1.1.7.1 Method 1: Reaction of Triorganogallium and Elemental Tellurium . . . . . . 1141

39.32.1.1.8 Indium Alkanetellurolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1142

39.32.1.1.8.1 Method 1: Reaction of Dipropyl Ditelluride with Trimesitylindium . . . . . . 1142

39.32.1.1.9 Magnesium Alkanetellurolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1142

39.32.1.1.9.1 Method 1: Reaction of Grignard Reagents with Elemental Tellurium . . . . 1142

39.32.1.1.10 Lithium Alkanetellurolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1142

39.32.1.1.10.1 Method 1: Reaction of Alkyllithiums with Elemental Tellurium . . . . . . . . . 1142

39.32.1.1.11 Sodium Alkanetellurolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1143

39.32.1.1.11.1 Method 1: Reduction of Dialkyl Ditellurides with Sodium Borohydride . . 1143

39.32.2 Product Subclass 2: Alkanetellurolates of Group 3–12 MetalsA. Polo and J. Real

39.32.2 Product Subclass 2: Alkanetellurolates of Group 3–12 Metals . . . . . . . . . . . 1145


39.32.2.1.1 Terminal Alkanetellurolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1145

39.32.2.1.1.1 Method 1: Reaction of a Metal Complex with a Main GroupAlkanetellurolate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1145

39.32.2.1.1.2 Method 2: Reaction of Telluroxozirconium Complexes with Haloalkanes 1146

LVIII Table of Contents


39.32.2.1.1.3 Method 3: Oxidative Addition of Dialkyl Tellurides, Dialkyl Ditellurides,or (Alkyltellanyl)silanes to a Metal . . . . . . . . . . . . . . . . . . . . . . . . . 1147

39.32.2.1.1.4 Method 4: Insertion of Tellurium into Metal—Carbon Bonds . . . . . . . . . . . 1148

39.32.2.1.2 m2-Alkanetellurolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1149

39.32.2.1.2.1 Method 1: Reaction of a Metal Complex with a Main GroupAlkanetellurolate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1149

39.32.2.1.2.1.1 Variation 1: From Metal Halide Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114939.32.2.1.2.1.2 Variation 2: From Metal Carbonyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . 115039.32.2.1.2.2 Method 2: Reaction of Bridging Coordinated Tellurides with

Electrophiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115239.32.2.1.2.3 Method 3: Solvothermal Reaction of Disodium Ditelluride with Metal

Carbonyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115539.32.2.1.2.4 Method 4: Reaction of Anionic Carbonyl Complexes with

Alkanetellurenyl Halides or (Alkyltellanyl)telluroniumCompounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1156

39.32.2.1.2.5 Method 5: Oxidative Addition of a Dialkyl Ditelluride or(Alkyltellanyl)phosphine to a Metal Complex . . . . . . . . . . . . . . . 1157

39.32.2.1.2.6 Method 6: Reaction of a Tellurolate–Metal Complex with a SecondMetal Complex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1158

39.32.2.1.2.7 Method 7: Insertion of Tellurium into Metal—Carbon Bonds . . . . . . . . . . . 1159

39.32.2.1.3 m3-Alkanetellurolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1159

39.32.2.1.3.1 Method 1: Reaction of Bridging, Coordinated Tellurides with anAlkylating Agent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1159

39.32.2.1.3.2 Method 2: Reaction of a Metal Salt with an (Alkyltellanyl)trimethylsilane 1160

39.33 Product Class 33: Acyclic Dialkyl TelluridesM. Segi

39.33 Product Class 33: Acyclic Dialkyl Tellurides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1163


39.33.1.1 Method 1: Synthesis from Hydrogen Telluride or Alkanetellurols . . . . . . . 116339.33.1.2 Method 2: Synthesis from Alkanetellurolates . . . . . . . . . . . . . . . . . . . . . . . . . 116539.33.1.2.1 Variation 1: By Reaction with Alkyl Halides for Symmetrical Telluride

Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116539.33.1.2.2 Variation 2: By Reaction with Alkyl Halides for Unsymmetrical Telluride

Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116639.33.1.2.3 Variation 3: By Reaction with Sulfonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116839.33.1.2.4 Variation 4: By Reaction with Lactones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117039.33.1.2.5 Variation 5: By Reaction with Epoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117039.33.1.3 Method 3: Reduction of Organotellurium(IV) Trichlorides or Dichlorides 117139.33.1.4 Method 4: Reduction of Acyclic Telluroxides or Tellurones . . . . . . . . . . . . . 117239.33.1.5 Method 5: Alkylation of Tellurium Tetrachloride . . . . . . . . . . . . . . . . . . . . . . . 1172

39.33.2 Applications of Product Class 33 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . . . 1173

39.33.2.1 Method 1: Use as Synthetic Equivalents for Organolithium Compounds 117339.33.2.2 Method 2: Use as a Catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1174

Table of Contents LIX


39.33.2.2.1 Variation 1: Debromination of vic-Dibromides . . . . . . . . . . . . . . . . . . . . . . . . . 117439.33.2.2.2 Variation 2: Synthesis of Vinyloxiranes from Aldehydes and Allyl Bromide 117439.33.2.3 Method 3: Use as a Reducing Agent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1175

39.34 Product Class 34: Acyclic Trialkyltelluronium Salts and DerivativesY. Tang and X.-L. Sun

39.34 Product Class 34: Acyclic Trialkyltelluronium Salts and Derivatives . . . . . . 1179


39.34.1.1 Method 1: Reaction of Dialkyl Tellurides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118039.34.1.2 Method 2: Reaction of Dialkyl Ditellurides . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118439.34.1.3 Method 3: Reaction of Dialkyltellurium Dihalides . . . . . . . . . . . . . . . . . . . . . 118439.34.1.4 Method 4: Reaction of Halooxatelluranes with Alkyllithium or

Grignard Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118539.34.1.5 Method 5: Reaction of Tellurium Tetrachloride with Alkyllithium

Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118539.34.1.6 Method 6: Reaction of Tellurium and Tellurolates . . . . . . . . . . . . . . . . . . . . . 118639.34.1.7 Method 7: Anion Exchange of Telluronium Salts . . . . . . . . . . . . . . . . . . . . . . 1186

39.35 Product Class 35: Alkanetellurenic Acids and Acyclic DerivativesT. Wirth

39.35 Product Class 35: Alkanetellurenic Acids and Acyclic Derivatives . . . . . . . . 1193

39.35.1 Product Subclass 1: Alkanetellurenic Acids and Esters . . . . . . . . . . . . . . . . . . . 1193

39.35.2 Product Subclass 2: Alkanetellurenyl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . 1193


39.35.2.1.1 Method 1: Synthesis Using Dibutyl Ditelluride . . . . . . . . . . . . . . . . . . . . . . . . 119339.35.2.1.2 Method 2: Synthesis Using Bis[tris(trimethylsilyl)methyl] Ditelluride . . . 1194

39.35.3 Product Subclass 3: (Alkyltellanyl)phosphines and Related Compounds . 1194


39.35.3.1.1 Method 1: Synthesis of (Alkyltellanyl)phosphines . . . . . . . . . . . . . . . . . . . . . 119439.35.3.1.2 Method 2: Synthesis of Trialkyl(methyltellanyl)phosphonium Salts . . . . . 119539.35.3.1.3 Method 3: Synthesis of Organo Tellurophosphates . . . . . . . . . . . . . . . . . . . . 1195

39.36 Product Class 36: Acyclic Di- and PolytelluridesR. Sato and T. Kimura

39.36 Product Class 36: Acyclic Di- and Polytellurides . . . . . . . . . . . . . . . . . . . . . . . . . 1197

39.36.1 Product Subclass 1: Symmetrical Dialkyl Ditellurides . . . . . . . . . . . . . . . . . . . 1197


39.36.1.1.1 Method 1: Reaction of Disodium Ditelluride with Alkyl Halides . . . . . . . . . 119739.36.1.1.2 Method 2: Electrolysis Followed by Alkylation . . . . . . . . . . . . . . . . . . . . . . . . . 119839.36.1.1.3 Method 3: Reaction of Tellurium with Organolithium Reagents . . . . . . . . 1199

LX Table of Contents


39.36.2 Product Subclass 2: Unsymmetrical Dialkyl Ditellurides . . . . . . . . . . . . . . . . . 1200


39.36.2.1.1 Method 1: Preparation by Electrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1200

39.37 Product Class 37: Telluriranes and DerivativesM. Saito and J. Nakayama

39.37 Product Class 37: Telluriranes and Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . 1203

39.38 Product Class 38: Telluretanes and DerivativesE. Block

39.38 Product Class 38: Telluretanes and Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . 1205


39.38.1.1 Synthesis by Ring-Closure Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1205

39.38.1.1.1 Method 1: Reaction of 1,3-Dihalides with Telluride Ion . . . . . . . . . . . . . . . . 120539.38.1.1.2 Method 2: Reaction of Dienes with Tellurium Halides . . . . . . . . . . . . . . . . . 120539.38.1.1.3 Method 3: Synthesis of a 1,2-Oxatelluretane from a 2-Lithio Alcoholate

and Tellurium Tetrachloride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1205

39.39 Product Class 39: Tellurolanes, Larger Rings, and Derivatives of VariousOxidation StatesR. Sato and T. Kimura

39.39 Product Class 39: Tellurolanes, Larger Rings, and Derivatives of VariousOxidation States . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1207

39.39.1 Product Subclass 1: Cyclic Alkanetelluronic Acid DerivativesR. Sato and T. Kimura

39.39.1 Product Subclass 1: Cyclic Alkanetelluronic Acid Derivatives . . . . . . . . . . . . 1209

39.39.2 Product Subclass 2: Cyclic Dialkyl Tellurones and DerivativesR. Sato and T. Kimura

39.39.2 Product Subclass 2: Cyclic Dialkyl Tellurones and Derivatives . . . . . . . . . . . 1211

39.39.3 Product Subclass 3: Cyclic Alkanetellurinic Acid DerivativesR. Sato and T. Kimura

39.39.3 Product Subclass 3: Cyclic Alkanetellurinic Acid Derivatives . . . . . . . . . . . . . 1213


39.39.3.1.1 Method 1: Cyclic Tellurinic Acid Esters by Oxidation of Bis(3-hydroxy-propyl) Ditelluride with tert-Butyl Hydroperoxide . . . . . . . . . . . 1213

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39.39.4 Product Subclass 4: Cyclic Dialkyl Telluroxides and DerivativesT. Shimizu and N. Kamigata

39.39.4 Product Subclass 4: Cyclic Dialkyl Telluroxides and Derivatives . . . . . . . . . . 1215


39.39.4.1.1 Method 1: Synthesis of Cyclic Dialkyltellurium Dihalides . . . . . . . . . . . . . . . 121539.39.4.1.2 Method 2: Synthesis of Cyclic Telluroxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121539.39.4.1.3 Method 3: Synthesis of Other Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1216

39.39.5 Product Subclass 5: Cyclic Alkanetellurolates of Group 1, 2, and 13–15MetalsN. Kambe

39.39.5 Product Subclass 5: Cyclic Alkanetellurolates of Group 1, 2, and 13–15Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1217


39.39.5.1.1 Method 1: Diels–Alder Cyclization of a Telluroxosilane with2-Methylbuta-1,3-diene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1217

39.39.6 Product Subclass 6: Cyclic Alkanetellurolates of Group 3–12 MetalsA. Polo and J. Real

39.39.6 Product Subclass 6: Cyclic Alkanetellurolates of Group 3–12 Metals . . . . . 1219


39.39.6.1.1 Method 1: Cyclic Ditellurolates from Bridging, Coordinated Tellurides . . 121939.39.6.1.1.1 Variation 1: By Reaction with Dihaloalkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . 121939.39.6.1.1.2 Variation 2: By Reaction with Diazomethane . . . . . . . . . . . . . . . . . . . . . . . . . . . 122039.39.6.1.2 Method 2: Cyclic Aminotellurolates by Reaction of an Alkylamino

Ditelluride with a Metal Complex . . . . . . . . . . . . . . . . . . . . . . . . . . 122039.39.6.1.3 Method 3: Cyclic Tellurolates with a M—C Bond by Reaction with

Tellurolates or Tellurium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1221

39.39.7 Product Subclass 7: Cyclic Dialkyl TelluridesM. Segi

39.39.7 Product Subclass 7: Cyclic Dialkyl Tellurides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1225


39.39.7.1.1 Method 1: Alkylation of Metal Tellurides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122539.39.7.1.1.1 Variation 1: With Dihaloalkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122539.39.7.1.1.2 Variation 2: With Bis(methanesulfonates) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122639.39.7.1.1.3 Variation 3: With Cyclic Ammonium Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122739.39.7.1.2 Method 2: Alkylation of Potassium Tellurocyanate . . . . . . . . . . . . . . . . . . . . 122739.39.7.1.3 Method 3: Reduction of Cyclic Tellurium Dihalides . . . . . . . . . . . . . . . . . . . . 122839.39.7.1.4 Method 4: Cycloaddition of Tellurocarbonyl Compounds . . . . . . . . . . . . . . 1230

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39.39.8 Product Subclass 8: Cyclic Trialkyltelluronium Salts and DerivativesY. Tang and X.-L. Sun

39.39.8 Product Subclass 8: Cyclic Trialkyltelluronium Salts and Derivatives . . . . . 1233


39.39.8.1.1 Method 1: Reaction of Cyclic Tellurides with Alkylating Agents . . . . . . . . 123339.39.8.1.2 Method 2: Ring-Closure Reaction of Aluminum Telluride with

Dihaloalkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123739.39.8.1.3 Method 3: Anion Exchange of Cyclic Telluronium Salts . . . . . . . . . . . . . . . . 1238

39.39.9 Product Subclass 9: Cyclic Alkanetellurenic Acid DerivativesT. Wirth

39.39.9 Product Subclass 9: Cyclic Alkanetellurenic Acid Derivatives . . . . . . . . . . . . 1243

39.39.10 Product Subclass 10: Cyclic Dialkyl Di- and PolytelluridesR. Sato and T. Kimura

39.39.10 Product Subclass 10: Cyclic Dialkyl Di- and Polytellurides . . . . . . . . . . . . . . . 1245

39.39.10.1 Synthesis of Product Subclass 10 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1245

39.39.10.1.1 Method 1: Electrosynthesis from Dihaloalkanes . . . . . . . . . . . . . . . . . . . . . . . 124539.39.10.1.1.1 Variation 1: Of 1,2-Ditellurolane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124539.39.10.1.1.2 Variation 2: Of Seven- and Eight-Membered Cyclic Ditellurides . . . . . . . . . . 124539.39.10.1.2 Method 2: Synthesis via Tellurocyanate Intermediates . . . . . . . . . . . . . . . . 124639.39.10.1.2.1 Variation 1: 1,2-Ditellurolane from 1,3-Dihaloalkanes . . . . . . . . . . . . . . . . . . 124639.39.10.1.2.2 Variation 2: 1,2-Ditellurolane from 1,3-Bis(tosyloxy)alkanes . . . . . . . . . . . . . 124739.39.10.1.3 Method 3: Synthesis of 1,2-Ditellurane from Dihaloalkanes and

Disodium Ditelluride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124839.39.10.1.3.1 Variation 1: In Dimethylformamide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124839.39.10.1.3.2 Variation 2: In Water/Benzene Using a Phase-Transfer Catalyst . . . . . . . . . . 1248

Keyword Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1251

Author Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1317

Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1379

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Documents

Volume39: Sulfur,Selenium,andTellurium · 2020. 7. 14. · 39.17 ProductClass17:AcyclicDialkylSelenoxidesandDerivatives T. Shimizu and N. Kamigata .....929 39.18 ProductClass18:Alkaneselenols