Novel Trends inElectroorganic SynthesisProceedings of the Second InternationalSymposium on Electroorganic Synthesis,Kurashiki, September 27—30, 1994and Pre-Symposium on Novel Aspects ofElectrogenerated Active Species,Okayama, September 24—25, 1994
Edited by
Sigeru Torii Okayama University, Okayama
1995
KODANSHATokyo
Contents
Preface v
List of Contributors xix
1. Reactive Species Formed by Electrochemical Electron Transfers andTheir Reaction Mechanisms
Determination of Redox Potentials of Radicals and Their Use in Synthesis andStudies of Reaction Mechanism 1
H. Lund
Formation and Reactivity of Diazo Radical Cations 7Y. Sawaki, K. Ishiguro, M. Ikeda and Y. Hattori
Electron Transfer Induced C-O Bond Breaking 11J. L. Rodriguez, M. G. Severin and E. Vianello
Regioselective Remote Functionalisation of Ketones : A Strong Parallelbetween Electrochemical and Free Radical Oxidation 15
E. I. Troyansky and G. I. Nikishin
New Advances in the Intramolecular Trapping of Anodically GeneratedRadical Cations 17
Z. Tesfai, D. G. New and K. D. Moeller
The Electroorganic Chemistry of C60 21D. H. Evans
Anodic Multi-Cyclization Processes : Synthesis and Mechanism 25J. Y. Becker and E. Shakkour
Photo-Induced Electron Transfer Reaction of Cyclopropanone Acetals withCarbonyl Compounds : Generation of /?-Keto Radical Species and ItsReactivity 29
M. Abe and A. Oku
n-cr Type Charge-Transfer Interaction of />-Quinone w-Dianions Generated atSequential Electroreduction Steps 31
N. Okumura and B. Uno
Anodically Generated Radical Cations of Organophosphorus Compounds inthe Reaction of Homolytic Hydrogen Abstraction 33
A. S. Romakhin, V. A. Zagumennov, A. N. Belousov and E. V. Nikitin
viii Contents
Reasons for Isotope Depletion during Syntheses of Deuterated Compounds byElectrochemical Reduction 35
M. Wahren and P. Kranke
Electrogeneration and Further Reactions of Carbon-Based cr-Radicals 37J. Grimshaw
Molecular Conversion Based on Multi-Electron Transfer System 41E. Tsuchida, K. Yamamoto and K. Oyaizu
Mechanism of Electroorganic Reaction in the Sealed 1.5V Metal-FreeAccumulator of New Type 45
I. Barsukov, V. Barsukov and T. Motronyuk
2. Role of the Halogen Atom in Electrosynthetic Reactions
Electroorganic Synthesis of Substituted Cyclopropanes 47M. N. Elinson, S. K. Feducovich, T. L. Lizunova and G. I. Nikishin
Recent Advances in the Synthesis of Chalcogeno Derivatives byElectrochemically Induced SRN1 Substitution 51
C. Degrand and M. Genesty
The Reaction of Olefinic Amines and Amidines with Electrogenerated andChemically Tailored Active Halogen Species 55
B. Daoust, P. Bouchard and J. Lessard
Products from Electrochemical Dimerization Reactions 59L. Rampazzo
Electrochemical Dehalogenation of Chlorinated Aromatics and Aliphatics-A Contribution to the Degradation of Xenobiotics 63
J. Voss
Use of Transition-Metal Complexes as Homogeneous and Polymer-BasedCatalysts for Electroorganic Synthesis 67
D. G. Peters, C. E. Dahm, D. Bhattacharya, A. L. Butler and M. S. Mubarak
A Convenient Electrochemical Synthesis of /J-Lactones 71K.-H. Schwarz, K. Kleiner, R. Ludwig and H. Schick
New Synthetic Possibilities of the Cathodic Reduction of «-Halo CarbonylCompounds and Derivatives 75
F. Barba
Electrochemical Preparation and Reactions of Some Af-ChlorosubstitutedCompounds 79
V. A. Petrosyan
Co(salen) and Ni(salen) Electrocatalyzed Reduction of Geminal Chlorides 83A. J. Fry, U. N. Sirisoma, A. H. Singh, A. Uglialoro, A. Lee, S. Kaufmanand T. Phanijphand
Contents ix
Electrochemistry of Hypervalent Compounds. First Electrosynthesis ofIodoarene Difluoride and Its Application to Indirect Anodic gem-Difluorination 85
T. Fujita and T. Fuchigami
Electrochemical Fluorination of Aldehydes and Ketones Using HF-BaseSolutions 87
N. Yoneda, S.-Q. Chen, T. Hatakeyama, S. Hara and T. Fukuhara
A Novel Synthesis of 2-Fluorothieno [2,3-b] Pyridines Using AnodicFluorination of Heterocyclic Sulfides as a Key Step 89
A. Konno, A. W. Erian and T. Fuchigami
Electrochemical Fluoro-Selenenylation of Olefins 91Y. Dan-oh, H. Matta and K. Uneyama
The Possibility of EC-Mechanism Realization at Fluoro-OlefinsElectrooxidation on Platinum and Glassy Carbon in Acids 93
V. A. Grinberg
Selective Anodic Mono- and Difluorination of Organic Molecules 95T. Fuchigami
Electrochemical Activation of Bromotrifluoromethane : a New Method toPrepare Trifluoromethylated Compounds 99
J.-M. Paratian, E. Labbe, S. Sibille, J.-Y. Nedelec and J. Perichon
Electrochemistry for Synthetic Organofluorine Chemistry 103K. Uneyama, Y. Dan-oh and H. Asai
3. Electrogenerated Base-Induced Reactions
The Effectiveness of Electrogenerated Bases 107J. H. P. Utley, Y. Gao, S. K. Ling-chung, S. Spriggs and M. F. Nielsen
Proton Transfer between Electrogenerated Carbanions and Acidic ParentCompounds 111
F. Maran and E. Vianello
Studies of the Properties of Electrogenerated Anions and Their Synthetic 115Applications
D. H. Evans
Electrogenerated Bases : Are They Useful for Organic Synthesis? 119M. E. Niyazymbetov and D. H. Evans
Aspects of Nitroalkene and Vinyl Sulfone Chemistry 123R. D. Little, M. Schwaebe and W. Russu
Preparation of Active Electrogenerated Base Catalyst in a Water-AproticSolvent System and Some Reactions 127
H. Kawafuchi
x Contents
The Effect of Electrolyte Concentration on the Reduction of Neutral andCharged Species 129
C. Amatore, M. F. Bento, C. Kristensen and M. I. Montenegro
4. Potentiality of Mediators in Electrolysis Systems
Electroreduction of Aliphatic Esters Using Mg and Sm as Mediators 133S. Kashimura, M. Ishifune, H. Ishida and T. Shono
Oxidative Free-Radical Additions of a-Nitro Ketones and a-Nitro Amides toAlkenes and Alkynes Mediated by Electrochemically RegenerableManganese(III) Acetate 135
R. Warsinsky and E. Steckhan
Heterocyclic o-Quinone as an Electrochemical Mediator for Enzymatic RedoxReactions 139
S. Itoh, H. Fukushima, M. Komatsu, Y. Ohshiro and S. Fukuzumi
A Novel Ru(VII)/Ru(IV) Mediator System for Electrooxidation of Alcohols 141S. Torii, A. Yoshida and H. Tanaka
Electrocatalytic Oxidation on Mediator-Modified Electrode 143T. Osa
Diastereoselective and Enantioselective Conversions at the Anode and theCathode 149
H. J. Schafer, B. Klotz-Berendes, M. Letzel, C. Zielinski, N. Schoo, T. Lohland U. Howeler
Oxidation of Dihydroxyalkanoates to 1,2,3 Tricarbonyl Compounds byIndirect Electrolysis Using 4-Bzotempo and Bromide Ion 155
T. Inokuchi, P. Liu and S. Torii
Selective Functionalization of Organic Compounds through ElectrogeneratedActive Species 157
I. Nishiguchi
Reactions of Electrogenerated Active Species with Biologically Active OrganicCompounds 161
V. Gromovaya, G. Shapoval
Fluoride Ion Mediated Anodic Alkoxylation of Organosulfur Compounds 163M. Sano, A. Konno, T. Nonaka and T. Fuchigami
Reactivity of Electrogenerated Superoxide Ion-A Biologically Active Species,with Organic Molecules 165
R. A. Misra, M. Singh and S. Dwivedi
Electrogeneration and Dismutation of Superoxide Ion in Aqueous Media 169T. Ohsaka, F. Matsumoto, T. Okajima, F. Kitamura and K. Tokuda
Aerobic Oxidation of Olefins Initiated by Electrogenerated HeteroatomRadical or Radical Cations 171
H. Tanaka, R. Kikuchi, H. Kanda and S. Torii
Contents xi
Electrochemical Investigation of Oxygenation Catalysts 173E. Eichhorn, A. Rieker, B. Speiser and H. Stahl
Oxidation of Alcohol by an Electrogenerated Active Species 175L.-M. Chen, Y.-L. Chen and T.-C. Chou
Indirect Organic Electrosynthesis Using a Flow Cell and an OrganometallicMediator Performed in an Excell Two Phase Process 177
C. Moinet, D. Floner and T. Jan
Electrochemical Rearrangement Reactions Mediated by Hydrophobic VitaminB12 in Nonaqueous Media 181
Y. Murakami, Y. Hisaeda, T. Ohno and T. Nishioka
Indirect Electroreductive Radical Cyclization and Addition Catalyzed byNi(II) Complexes 185
S. Ozaki, S. Mitoh, Y. Urano and H. Ohmori
The Formation of P-C Compounds from P-Cl Compounds by Ni(dipy)2
Complex Electrocatalysis 187Y. H. Budnikova, A. M. Yusupov and Y. M. Kargin
Electrochemical Synthesis of Unusual Species Useful for HomogeneouslyCatalyzed Organic Reactions 189
J. F. Carpentier, Y. Castanet, E. Monflier, S. Pellegrini and A. Mortreux
Ni/Pb Bimetal-Redox Mediated Reductive Addition/Cyclization ofAllenecarboxylate with Allyl Bromide in a Electrolysis Media 193
H. Tanaka, S. Sumida, K. Sorajo and S. Torii
Pd(O)/Pd(II)-Mediated Electroreductive Cyclization of A'-Alkenyl-2-Bromoanilines 195
H. Tanaka, Q. Ren and S. Torii
5. Novel Aspects of Organometallic Compounds in Electrosynthesis
Reactions of Electrogenerated Odd-Electron Organometallic Compounds.Reductive Coupling of <r-Ethynyl Transition Metal Complexes 197
L. I. Denisovich, N. A. Ustynyuk, M. G. Peterleitner, S. M. Peregudovaand V. N. Vinogradova
A Novel Synthetic Metal Catalytic System for Oxidation 199T. Hirao, M. Higuchi and I. Ikeda
Electrochemical Synthesis of Carbonyl Cobaltate Moieties: Their Applicationin Ring-Opening of Oxiranes and Alkoxycarbonylation of Dichloromethane 201
P. Suisse, S. Pellegrini, E. Monflier, A. Mortreux, J. F. Carpentier andY. Castanet
The Electrogeneration and Synthetic Aspects of the Collman Reagent,Fe(CO)4
2" 2 0 5
C. Amatore, J.-N. Verpeaux and S. U. Pedersen
xii Contents
Nickel-Complex Catalysis in the Electrochemical Cross-Coupling betweenAromatic Halides and Activated Alkyl Halides : Search for the Occurence ofa Double Oxidative Addition 209
M. Durandetti, S. Sibille, J.-Y. Nedelec and J. Perichon
Electroreduction of Organic Compounds Using Chemically Reactive MgElectrode 213
S. Kashimura, M. Ishifune and T. Shono
Activation of Aryl Triflates by Palladium or Nickel Complexes and ElectronTransfer. Application to the Synthesis of Biaryls and Aromatic CarboxylicAcids 217
A. Jutand, A. Mosleh and S. Negri
Electron Transfer Reactions of Group 14 Organometallic Compounds 221K. Mizuno, Y. Ishii, T. Ohshika, Y. Otsuji and H. Inoue
The Electroorganic Syntheses by Using Low Valency Cobalt Complex 223T.Inokuchi
Electrochemistry and Organometallic Catalysis : Learning fromOrganometallic Chemistry to Increase Electrochemical Selectivity 227
C. Amatore
Organonitrogen Compounds from Molecular Nitrogen via ElectrochemicalReactions of Mo and W Complexes 231
C. J. Pickett, M. L. Abasq and S. K. Ibrahim
6. Electrochemical Conversion of Carbonyl Compounds
Stereoselective Electrohydrodimerization : Cathodic Reduction of Cinnamates 235J. H. P. Utley, C. I. de Matteis, M. Motevalli, M. Giillii, O. Hammerich,A. Hussain and M. F. Nielsen
Electroreductive Coupling of O-Benzoylcyanohydrin with Aldehydes 239T. Ito, N. Yamaguchi and I. Nishiguchi
Facile Isoprenylation and Allylation of Carbonyl Compounds withElectrogenerated Reactive Zinc 241
M. Tokuda
Electrochemical Oxidation of a,a,w,&j-Alkanetetracarboxylate Esters 245S. K. Feducovich, M. N. Elinson and G. I. Nikishin
Electrochemical Activation of Carbonylation Processes 247F. Carbone, G. Filardo, A. Galia, S. Gambino, P. Giannoccaro andG. Silvestri
Electroorganic Processes under Ultrasonic Irradiation 251T. Nonaka, M. Atobe, P.-C. Chen, K. Matsuda and H. Fujiwara
Electrosynthesis of Adipic Acid 255J. Kodera, S. Ito, A. Kitani and K. Sasaki
Contents xiii
Synthesis of Unsaturated Lactones Utilizing Electrochemical Carboxylation 257M. Tokuda, T. Kabuki, M. Yoshikawa, T. Tokuhashi, M. Miyazawa,K. Orito and H. Suginome
7. Elaborate Functionalization of Organic Compounds inElectrolytic Media
Electrochemical Transformation of Olefins : Synthetic Application 259G. I. Nikishin
Anodic Oxidation of Tyrosine Derivatives 263A. Rieker, A. Hutinec, E.-L. Dreher, A. Ziogas and M. El-Mobayed
Synthetic Studies on Natural Products Using Electrochemical Method as aKey Step 265
S. Yamamura
Role of Some Electrode Materials, Configuration, Solvent Composition andElectronegative Substituents on Reduction of Nitrobenzenes 269
P. Zuman and C. Karakus
Indirect Electro-Oxidation of Substituted Toluenes and Hydroquinones 271P. Bouchard and A. Velin
Electrosynthesis of Chromenes from 2-(l-Bromo-l-Methylethyl) Benzofurans 275M. Tsukayama, H. Utsumi and A. Kunugi
Electrooxidaton of 1,4,5,8-Tetramethoxynaphthalenes, Leading to Shikonin 277S. Torii, K. Akiyama and T. Inokuchi
Electrochemical Amination of Aromatic Compounds in Sulfuric AcidElectrolytes 279
Y. Lisitsyn and Y. Kargin
Electrochemical Deamination of Aromatic Amines 281S. Torii, H. Okumoto, H. Satoh, T. Minoshima and S. Kurozumi
A Novel Electrochemical Route to o-Allyl- and o-Allenylphenols 283N. Bhuvaneswari, K. K. Balasubramanian and C. S. Venkatachalam
Electrochemical Approach to Isodityrosine and Related Natural Products 285S. Nishiyama, M. H. Kim and S. Yamamura
Anodic Oxidation of Aromatic Acids 287S. Rosca, M. Ungureanu and O. Vrublevschi
Highly Chemoselective Deprotection of an Acyl Group of Esters byElectro-Organic Reduction 289
T. Itoh, H. Ohara and S. Emoto
Electrochemical, Photochemical and Chemical Cyclization of Some ArylHalides : Development of the Electrochemical Process at Solid Electrodes 291
S. Donnelly, J. Grimshaw and J. Trocha-Grimshaw
xiv Contents
Electrooxidative Cyclization Using Group 14 Metals 295J. Yoshida, K. Takeda, Y. Ishichi and S. Isoe
Electroreductive Coupling and Cyclization Reactions 299R. D. Little, H. Bode, T. Bregant and M. Schwaebe
Radical Tandem Cyclizations 303A. Matzeit and H.J. Schafer
Anodic Oxidation in Heterocyclic Chemistry 307I. Tabakovic
Electrochemical Nitrations 311A. J. Bloom and J. M. Mellor
Electrochemical Generation of 1,3-Dipole 315S. Torii, H. Okumoto and A. Genba
Anodic Amide Oxidations : New Routes to Conformationally RestrictedPeptide Mimetics 317
F. Cornille, Y. M. Fobian, W. Li, U. Slomczynska, D. D. Beusen,G. R. Marshall and K. D. Moeller
The Selective Reduction of Aliphatic and Aromatic Nitro Compounds :Scope of the Electrochemical Method 321
J.-M. Chapuzet, B. Cote, M. Lavoie, E. Martel, C. Raffin and J. Lessard
Preparation of 4-Trimethylsilylazetidin-2-ones and Their ElectrochemicalOxidation 325
K. Suda, K. Hotoda and T. Takanami
Electrosynthesis of Cyclic Compounds 327P. M. Bersier, J. Bersier and L. Carlsson
Electrochemical Oxidation of Organic Compounds in Trifluoroethanol 329Y. Matsumura
8. Characteristic Features of Hetero Atom Compounds inElectroorganic Synthesis
Electrochemical Reactivity of Selenium and Silicon Organic Compounds 333V. Jouikov
Electrochemical Functionalization of Sulfide : a-Acetoxylation and ItsRelated Reactions 335
J. Nokami, S. Fukutake, M. Yoriyasu, T. Fukushima, N. Kuwata andM. Ikuta
Synthesis of 1,3-Oxathiolans as a Thioribose Precursor by Electrochemical^-Oxidation of Sulfides 337
J. Nokami, K. Ry6kume, M. Honda and J. Inada
Contents xv
Electrooxidative Intramolecular Cyclization of Functionalized SulfidesGiving Five-Membered Rings 339
M. Kimura, T. Hayakawa and Y. Sawaki
Photoisomerization and New Electrochemistry of Azobenzene Derivatives 341A. Fujishima
Synthetic Application of Acyl- and Alkoxy-Phosphonium Ions 345H. Ohmori, T. Maki and H. Maeda
A Novel View on Electrochemical Oxidation Mechanism ofOrganophosphorus Compounds 349
E. V. Nikitin, A. S. Romakhin, F. M. Palyutin, V. A. Zagumennov andY. A. Ignatiev
Electrochemical Bromodifluoromethyl-Selenation of Olefins 351K. Uneyama and H. Asai
Electrochemical Syntheses of Polygermanes 353M. Okano, T. Toriumi, K. Takeda and H. Hamano
9. Collaboration of Polymer Materials and Electrochemical Methods
Reactions of Electrogenerated Active Species with Low- and High-MolecularOrganic Compounds 355
G. Shapoval
On the Way to a Redoxactive Polyelectrolyte System 359R. Wend and E. Steckhan
Reactions Using Electrodes Coated with Poly(Amino Acids) Used as Supportsfor Iron Catalysts 363
A. T. M. Kane, M. Devenney, J. Grimshaw and J. Trocha-Grimshaw
Undoping of Electropolymerized Polymers and Electrode Corrosion 365K. Uehara, T. Serikawa, T. Ichikawa, M. Tsunooka, S. Yoshikawa andS. Ehara
Electrocatalysis of Poly(2,5-Dihydroxyaniline) Synthesized byElectropolymerization in Aqueous Solutions 367
M. Morita, H. Takase, M. Ishikawa and Y. Matsuda
Effects of Para-Phenylenediamine on Electropolymerization of Aniline 369H. Tang, A. Kitani, S. Maitani, H. Munemura and M. Shiotani
Synthesis of New Conductive Polypyrroles Annulated with PolycyclicAromatic Compounds 371
N. Ono, H. Hironaga, K. Ono and T. Ogawa
Incorporation of Metal Microparticles into Poly(;V-Substituted Pyrrole) FilmElectrodes 373
N. Takano, M. Nakabayasi and N. Takeno
xvi Contents
Electrochemical Behavior of the Polyphosphazene Polymers with PendantHydroxymethylferrocenyl Groups in Solution and Films 375
D. Kraiter, P. Wisian-Neilson and A. L. Crumbliss
Modified Electrodes by Polypyrrole Ruthenium Polypyridyl Complexes Filmsas Catalysts in Oxidations of Alcohols 379
A. Rossi, J. R. Romero and W. F. de Giovani
Electrochemical Functionalization of Fluorine-Containing Polymers 381A. Pud, G. Shapoval and O. Mikulina
10. Frontiers of Bio-Electrochemistry
Electroenzymatic Synthesis 383B. Brielbeck, M. Frede, G. Hilt, L. Kramer and E. Steckhan
Microfabrication and Characterization of Enzyme-Patterned Surfaces byScanning Electrochemical Microscopy 387
T. Matsue, H. Shiku, T. Takeda and I. Uchida
Electrochemical Oxidation of Benzyl Alcohol to Benzaldehyde Mediated by aFlavin Coenzyme Analogue in Acetonitrile 389
M. Ishikawa, H. Okimoto, M. Morita and Y. Matsuda
Photoswitching of NAD+-Mediated Enzyme Reaction ThroughPhoto reversible Antigen-Antibody Reaction 391
T. Hohsaka and M. Sisido
Electrochemically Activated Ferredoxin for Bioelectrocatalytic Reactions 393I. Taniguchi
Interfacial Electron Transfer and Bioelectrocatalysis of the Redox CoenzymesAdsorbed on Metal Oxide Electrodes 397
H. Shinohara, M. Sisido and H. Akaike
Surface Modification of an Indium Oxide Electrode for Direct ElectronTransfer of Ferredoxin 399
I. Taniguchi, K. Iwakiri, T. Kawakatsu, H. Ishida, A. Miyahara andK. Nishiyama
Selective Synthesis of Hydroxy Acids by Electrochemical Regeneration ofNADH at Enzyme-Modified Electrodes 401
A. J. Fry, S. B. Sobolov, M. D. Leonida, J. Kim, K. I. Voivodov andF. Mckinney
Construction and Photoresponse of Gold and ITO Electrodes Modified withRuthenium Complexes and Viologens 405
S. Yamada, H. Kohrogi and T. Matsuo
In Situ Raman Study on the Behavior of Propylviologen Incorporated intoNafion-Coated Ag Electrode 407
M. Inaba, Y. Osa and Z. Ogumi
Contents xvii
Organic Electrosyntheses on Continuously in situ Modified Cathodes 409A. Savall
Enantioselective Synthesis of Lactate from Pyruvate Using Cysteine-ModifiedCdS Microcrystals 411
H. Yoneyama, R. Nakamura and S. Kuwabata
Electrode Reaction Rates of C-Type Cytochromes at Thiol Modified GoldElectrode 415
Z. Q. Feng, S. Imabayashi, T. Kakiuchi and K. Niki
Electrochemically Generated Luminescence of Luminol and Us Applicationfor Biosensing 419
M. Aizawa
11. Application of Electrochemical Methods
An Electrochemical Study of the Reduction of 4-Formyl-3-Phenylsydnone onMercury Glassy Carbon Electrodes 423
L.-H. Wang and H.-J. Tien
Electrochemistry for Materials Manufacture and Waste Treatment 425P. M. Bersier, L. Carlsson and J. Bersier
Electroorganic Reactions Induced by a DC Glow Discharge Plasma 427M. Tezuka and M. Iwasaki
Fluidised Bed Reactors and Electrode Materials for Electrosynthesis 429K. Kazdobin
Super Reduction with Oxygen-Lattice Defect Ferrite 431T. Korenaga
Electrochemical and Photocatalytic Bleaching of Methyl Orange 433T.-C. Chou, L.-C. Chen and C.-F. Chou
Industrial Organic Electrosynthesis - Opportunities and Challenges forEthylene Glycol 437
N. L. Weinberg, G. D. Zappi, J. D. Genders and D. Pletcher
Experimental Study of Reaction Selectivity Improvement for Reduction ofNitrobenzene in a Packed-Bed Electrode Reactor under Periodic-CurrentControl 441
X.-Q. Yang, P. Ding and W.-K. Yuan
Subject Index 443