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