Organic Electrochemistry

1716 Pages·2015·115.6 MB·English

by  Ole Hammerich, Bernd Speiser (eds.)

F I F T H E D I T I O N
ORGANIC
ELECTROCHEMISTRY
R E V I S E D A N D E X P A N D E D
© 2016 by Taylor & Francis Group, LLC

F I F T H E D I T I O N
ORGANIC
ELECTROCHEMISTRY
R E V I S E D A N D E X P A N D E D
EDITED BY
Ole Hammerich
University of Copenhagen, Copenhagen, Denmark
Bernd Speiser
Universität Tübingen, Tübingen, Germany

Boca Raton London New York
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Contents
Preface...............................................................................................................................................ix
Acknowledgments...........................................................................................................................xiii
Editors...............................................................................................................................................xv
Contributors....................................................................................................................................xvii
Section i Fundamentals and Methods
Chapter 1 Basic.Concepts..............................................................................................................3
Christian Amatore
Chapter 2 Techniques.for.Studies.of.Electrochemical.Reactions.in.Solution..............................97
Ole Hammerich and Bernd Speiser
Chapter 3 In Situ.Spectroelectrochemistry.of.Organic.Compounds.........................................169
Peter Rapta, Evgenia Dmitrieva, Alexey A. Popov, and Lothar Dunsch
Chapter 4 Surface.Techniques...................................................................................................191
Mohamed M. Chehimi and Jean Pinson
Chapter 5 Application.of.Digital.Simulation.............................................................................205
Bernd Speiser
Chapter 6 Theoretical.Calculation.of.Reduction.Potentials.......................................................229
Junming Ho, Michelle L. Coote, Christopher J. Cramer, and Donald G. Truhlar

Section ii General Preparative Aspects
Chapter 7 Preparative.Electrolysis.on.the.Laboratory.Scale.....................................................263
Jakob Jörissen and Bernd Speiser
Chapter 8 Application.of.Ionic.Liquids,.Emulsions,.Sonication,.and.Microwave.Assistance......331
John D. Watkins and Frank Marken
v
© 2016 by Taylor & Francis Group, LLC
vi Contents
Chapter 9 Combinatorial.Electrochemistry.and.Miniaturization..............................................345
Kevin D. Moeller
Chapter 10 Relations.between.Micro-.and.Macrophenomena.....................................................371
Christian Amatore
Section iii electron transfers and concerted Processes
Chapter 11 Influence.of.Molecular.and.Medium.Effects.on.Two-Electron.Processes................395
Kevin Lam and William E. Geiger
Chapter 12 Electrochemically.Driven.Supramolecular.Devices.................................................433
Paola Ceroni, Alberto Credi, and Margherita Venturi
Chapter 13 Proton-Coupled.Electron.Transfers...........................................................................481
Cyrille Costentin, Marc Robert, and Jean-Michel Savéant
Chapter 14 Dissociative.Electron.Transfers.................................................................................511
Cyrille Costentin, Marc Robert, and Jean-Michel Savéant
Chapter 15 Electron.Transfer–Catalyzed.Reactions....................................................................531
Kazuhiro Chiba and Yohei Okada
Section iV organic electrochemical Reaction types
Chapter 16 Cleavages.and.Deprotections....................................................................................559
Ole Hammerich

Chapter 17 Reductive.Coupling...................................................................................................621
James H.P. Utley, R. Daniel Little, and Merete Folmer Nielsen
Chapter 18 Oxidative.Coupling...................................................................................................705
Hans J. Schäfer
Chapter 19 Oxidative.Substitution.and.Addition.Reactions........................................................775
Ole Hammerich and James H.P. Utley
Chapter 20 Fluorination...............................................................................................................807
Toshio Fuchigami and Shinsuke Inagi
© 2016 by Taylor & Francis Group, LLC
Contents vii
Section V electrochemical conversions of organic compounds
Chapter 21 Electrochemistry.of.Fullerenes,.Derivatives,.and.Related.Compounds....................829
Frederic Melin, Lourdes E. Echegoyen, and Luis Echegoyen
Chapter 22 Aliphatic.and.Aromatic.Hydrocarbons:.Reduction...................................................861
Jürgen Heinze
Chapter 23 Oxidation.of.Hydrocarbons.......................................................................................891
Ole Hammerich
Chapter 24 Activation.of.the.Carbon–Halogen.Bond..................................................................917
Armando Gennaro, Abdirisak Ahmed Isse, and Patrizia Romana Mussini
Chapter 25 Aliphatic.and.Aromatic.Halides:.Conversions..........................................................941
Dennis G. Peters
Chapter 26 Oxygen-Containing.Compounds:.Alcohols,.Ethers,.and.Phenols............................981
Robert Francke, Thomas Quell, Anton Wiebe, and Siegfried R. Waldvogel
Chapter 27 Sulfur-,.Selenium-,.and.Tellurium-Containing.Compounds...................................1035
Richard S. Glass
Chapter 28 Aliphatic.Nitrogen–Containing.Compounds:.Amines,.Amino.Alcohols,.
and Amino.Acids....................................................................................................1103
Osamu Onomura
Chapter 29 Aromatic.Nitrogen–Containing.Compounds...........................................................1121
Jan S. Jaworski
Chapter 30 Reduction.of.Nitro.Compounds.and.Related.Substrates..........................................1149
Ole Hammerich
Chapter 31 Reduction.of.Aldehydes,.Ketones,.and.Azomethines.............................................1201
Jiří Ludvík
Chapter 32 Reductions.of.Carboxylic.Acids.and.Derivatives....................................................1249
Rolf Breinbauer and Martin Peters
Chapter 33 Oxidation.of.Carboxylic.Acids.and.Derivatives.....................................................1267
Hideo Tanaka, Manabu Kuroboshi, and Sigeru Torii
© 2016 by Taylor & Francis Group, LLC
viii Contents
Chapter 34 Heterocyclic.Compounds........................................................................................1309
Fructuoso Barba and Belen Batanero
Chapter 35 Organoelemental.Compounds.................................................................................1357
Jun-ichi Yoshida, Toshiki Nokami, and Seiji Suga
Chapter 36 Organometallic.Compounds.as.Tools.in.Organic.Electrosynthesis........................1393
Anny Jutand
Section Vi Stereochemical and Biological Aspects
Chapter 37 Electrosynthesis.of.Bioactive.Materials..................................................................1435
Randi K. Gbur and R. Daniel Little
Chapter 38 Stereochemistry.of.Organic.Electrode.Processes...................................................1461
Toshio Fuchigami and Shinsuke Inagi
Chapter 39 Electroenzymatic.Synthesis.....................................................................................1511
Christina Kohlmann and Stephan Lütz
Chapter 40 Electrochemical.Modeling.of.Biological.Processes................................................1543
Richard D. Webster
Section Vii Surface confined Systems
Chapter 41 Electrochemistry.of.Conducting.Polymers.............................................................1571
Jürgen Heinze

Chapter 42 Surface-Bound.and.Immobilized.Molecules..........................................................1605
Jean Pinson
Section Viii Special Applications
Chapter 43 Electrogenerated.Bases.and.Nucleophiles...............................................................1625
James H.P. Utley, Merete Folmer Nielsen, and Peter B. Wyatt
Chapter 44 Electrocatalytic.Hydrogenation...............................................................................1657
Jean Lessard
Index.............................................................................................................................................1673
© 2016 by Taylor & Francis Group, LLC
Preface
Organic.electrochemistry.is.concerned.with.the.reduction.and.oxidation.of.organic.molecules.at.
electrodes..Although.it.is.now.more.than.200 years.ago.that.the.so-called.Volta.pile.was.discov-
ered,.it.was.not.until.1830–1850.that.investigations.of.organic.electrochemical.processes,.pioneered.
by.Faraday.and.Kolbe,.were.established.as.a.research.area.in.their.own.right..Toward.the.end.of.
the. nineteenth.century,.investigators.such.as.Tafel.and.Haber.made.significant.contributions.to.the.
present.knowledge.of.organic.electrode.processes..Haber,.for.instance,.in.his.now.famous.paper.
on.the.reduction.of.nitrobenzene.(F..Haber,.Z. Elektrochem..1898,.4,.506).recognized.the.signifi-
cance.of.the.electrode.potential.in.the.following.words:.“Oxydations-.und.Reduktionsprozesse.hän-
gen.in.erster.Linie.von.dem.Potential.der.Elektrode.ab,.an.welcher.sie.ablaufen,.und.Stromdichte,.
Stromdauer.und.Elektrodenmaterial.sind.nur.insofern.bedeutsam,.als.sie.das.Elektrodenpotential.
und.seine.Änderungen.im.Gang.der.Elektrolyse.bestimmen.”.(“Oxidation.and.reduction.processes.
primarily.depend.on.the.potential.of.the.electrode.at.which.they.proceed,.and.current.density,.cur-
rent.duration,.and.electrode.material.are.only.important.insofar.as.they.determine.the.electrode.
potential.and.its.changes.during.the.electrolysis.”).The.application.of.electrolysis.as.a.means.of.
preparing.organic.compounds.continued.in.the.first.half.of.the.twentieth.century..This.development.
took.place.along.with.the.development.of.new.electrochemical.techniques.for.the.study.of.electrode.
processes,.for.instance,.polarography.at.the.dropping.mercury.electrode.introduced.by.Heyrovsky.
in.the.early.1920s..Other.important.contributions.were.due.to.Lingane,.Kolthoff,.Laitinen,.and.
Delahay..Later,.Hickling’s.potentiostat.(A..Hickling,.Trans. Faraday Soc. 1942,.38, 27) as.an.exper-
imental.tool.to.control.experiments.led.into.the.computerization.era.
Most.of.the.work.reported.before.World.War.II.was.carried.out.in.aqueous.electrolyte.solu-
tions..This.situation.changed.after.the.war,.and.since.the.mid-1950s,.the.attention.has.been.focused.
mostly.on.the.application.of.nonaqueous.solvents..This.has.allowed.for.the.detection.of.the.primary.
intermediates,.typically.radical.anions.and.radical.cations,.and.for.the.study.of.their.reactions..The.
theoretical.foundations.for.the.analysis.of.kinetics.and.mechanisms.by,.for.instance,.cyclic.voltam-
metry.and.related.techniques.were.mostly.published.in.the.1960s.and.1970s..The.application.of.such.
techniques.has.resulted.in.a.steadily.increasing.understanding.of.the.kinetics.and.mechanisms.of.
organic.electrochemical.processes.
Facing.the.fact.that.thousands.of.organic.electrochemical.processes.are.now.known,.it.is.striking.
that.most.often.the.only.electrochemical.reaction.to.be.mentioned.in.a.typical.organic.chemistry.
textbook.is.the.oxidation.of.an.organic.carboxylic.acid.R-COOH.to.the.corresponding.dimeric.
alkane.R-R.reported.by.Kolbe.as.early.as.1849..Also,.it.is.often.overlooked.that.reductions.by.met-
als.involving.radical.anions.as.intermediates.are.intimately.related.to.cathodic.reductions..And.
most.frequently,.radical.cations.are.not.mentioned.at.all,.except,.of.course,.in.the.context.of.mass.
spectrometry!.This.problem,.that.organic.electrochemistry.has.had.difficulties.in.penetrating.into.
the.organic.chemistry.curriculum,.was.pointed.out.already.in.the.preface.to.the.first.edition.of.this.
book..Unfortunately,.not.much.has.changed.in.the.more.than.40 years.that.have.elapsed.between.
that.edition.and.this.fifth.edition.
The.knowledge.of.organic.electrochemistry.had.in.the.1960s.and.the.early.1970s.matured.to.the.
point.where.the.time.was.ripe.for.the.first.edition.of.Organic Electrochemistry.(M.M..Baizer,.ed.,.
Organic Electrochemistry,.Marcel.Dekker:.New.York,.1973)..The.editor.was.Manual.M..Baizer,.
well.known.for.his.contributions.to.preparative.organic.electrochemistry,.first.of.all.the.develop-
ment.of.the.electrohydrodimerization.of.acrylonitrile.into.a.highly.successful.industrial.process.for.
the.manufacture.of.adiponitrile..Baizer.set.the.standards.for.the.book.that.was.organized.to.include.
chapters.both.on.the.electrochemical.reduction.and.oxidation.of.specific.classes.of.compounds.and.
ix
© 2016 by Taylor & Francis Group, LLC
x Preface
on.specific.types.of.electrode.processes..This.approach.obviously.led.to.some.overlap,.a.problem.that.
Baizer.touched.upon.in.the.following.words:.“It.has.become.routine,.at.least.for.reviewers,.to.point.
out.that.in.a.multi-authored.book.there.is.overlap.of.material,.non-uniformity.of.style,.repetition.etc..
This.book.was.not.hastily.assembled,.and.there.was.adequate.time.to.achieve.uniformity.if.that.had.
been.desired..But.the.material.was.deliberately.organized.so.that.a.given.segment.might.appear.in.
two.or.more.contexts.and,.further,.where.unanimity.of.opinion.does.not.exist,.more.than.one.current.
viewpoint.might.be.expressed.”.The.same.basic.philosophy.was.followed.in.the.organization.of.the.
second.(Baizer,.M.M.,.Lund,.H.,.eds.,.Organic Electrochemistry,.Marcel.Dekker:.New York,.1983),.
third.(Lund,.H.,.Baizer,.M.M.,.eds.,.Organic Electrochemistry,.Marcel.Dekker:.New.York,.1991),.
fourth.(Lund,.H.,.Hammerich,.O.,.eds.,.Organic Electrochemistry,.Marcel.Dekker:.New.York,.2001).
editions,.and.now.for.this.fifth.edition..Owing.to.this.intentional.overlap.between.chapters,.the.reader.
is.encouraged.to.use.the.index.to.find.details,.in.addition.to.those.found.in.a.given.chapter,.of.the.
electrochemistry.of.a.specific.compound.or.a.class.of.compounds..Also,.some.formal.variations.that.
reflect.common.usage.by.different.authors.have.not.been.brought.into.line,.for.example,.the.use.of.“e”.
or.“e−”.for.the.electron.or.the.nomenclature.of.electrochemical.mechanisms.(“ECE”.vs..“eCe,”.etc.).
The.progress.in.organic.electrochemistry.that.has.taken.place.since.the.appearance.of.the.fourth.
edition.is.reflected.by.the.organization.of.this.edition..Organic.electrochemical.reactions.are.rather.
complex.with.electron.transfers.and.transport.processes.interwoven.with.bond.breaking.and.forming.
reaction.steps..As.a.consequence,.different.perspectives.have.developed.over.the.years.and.organic.
electrochemistry.may.be.discussed.following.different.lines.of.thought..Moreover,.organic.electro-
chemical.reactions.are.often.integrated.into.more.complicated.synthetic.strategies.and.advanced.
chemical.reasoning.or.are.applied.to.complex.materials.and.structures..Consequently,.it.was.decided.
to.present.the.field.as.follows..After.an.introduction.of.some.basic.and.technical.aspects,.the.reac-
tion.step.that.distinguishes.organic.electrochemistry.from.classical.organic.reactions,.the.electron.
transfer.to.and.from.organic.molecules,.is.described.and.its.most.important.variants.are.presented..
Second,.the.importance.of.electron.transfers.for.the.initiation.of.various.organic.electrochemical.
reaction.types.(follow-up.reactions).is.emphasized..Third,.the.electrochemical.transformations.of.
organic.compounds.are.systematically.presented.according.to.the.type.of.starting.materials..Finally,.
cases.where.organic.electrochemistry.forms.an.integral.part.in.a.wider.context.of.chemical.research.
(e.g.,.in.biological.or.materials.science).are.discussed.
In.comparison.with.the.fourth.edition,.the.following.major.changes.have.been.made.to.this.
edition:
Sixteen.new.chapters.have.been.included..These.are:
•. Chapter.3:.In Situ.Spectroelectrochemistry.of.Organic.Compounds.by.Peter.Rapta,.Evgenia.
Dmitrieva,.Alexey.A..Popov,.and.Lothar.Dunsch
•. Chapter.4:.Surface.Techniques.by.Mohamed.M..Chehimi,.and.Jean.Pinson
•. Chapter.5:.The.Application.of.Digital.Simulation.by.Bernd.Speiser
•. Chapter.6:.Theoretical.Calculation.of.Reduction.Potentials.by.Junming.Ho,.Michelle.L..
Coote,.Christopher.J..Cramer,.and.Donald.G..Truhlar
•. Chapter.8:.The.Application.of.Ionic.Liquids,.Emulsions,.Sonication,.and.Microwave.
Assistance.by.John.D..Watkins.and.Frank.Marken
•. Chapter.9:.Combinatorial.Electrochemistry.and.Miniaturization.by.Kevin.D..Moeller
•. Chapter.11:.Influence.of.Molecular.and.Medium.Effects.on.Two-Electron.Processes.by.
Kevin.Lam.and.William.E..Geiger.
•. Chapter.12:.Electrochemically.Driven.Supramolecular.Devices.by.Paola.Ceroni,.Alberto.
Credi,.and.Margherita.Venturi
•. Chapter.13.and.14:.Proton-Coupled.Electron.Transfers.and.Dissociative.Electron.Transfers.
by.Cyrille.Costentin,.Marc.Robert,.and.Jean-Michel.Savéant
•. Chapter.15:.Electron.Transfer.Catalyzed.Reactions.by.Kazuhiro.Chiba.and.Yohei.Okada
© 2016 by Taylor & Francis Group, LLC