Catalysis in Asymmetric Synthesis

410 Pages·2009·3.11 MB·English

by  Caprio V.

P1:SFK/XXX P2:SFK/XXX QC:SFK/XXX T1:SFK
fm JWBK273-Caprio November25,2008 9:49 Printer:Yettocome
Catalysis in Asymmetric Synthesis
Second Edition
i
P1:SFK/XXX P2:SFK/XXX QC:SFK/XXX T1:SFK
fm JWBK273-Caprio November25,2008 9:49 Printer:Yettocome
PostgraduateChemistrySeries
A series designed to provide a broad understanding of selected growth areas of
chemistry at postgraduate student and research level. Volumes concentrate on
materialinadvanceofanormalundergraduatetext,althoughtherelevantback-
groundtoasubjectisincluded.Keydiscoveriesandtrendsincurrentresearchare
highlighted,andvolumesareextensivelyreferencedandcross-referenced.Detailed
andeffectiveindexesareanimportantfeatureoftheseries.Insomeuniversities,
theserieswillalsoserveasavaluablereferenceforfinalyearhonoursstudents.
EditorialBoard
ProfessorJamesCoxon(Editor-in-Chief),DepartmentofChemistry,University
ofCanterbury,NewZealand.
ProfessorPatBailey,DepartmentofChemistry,UniversityofManchester,UK.
ProfessorLesField,SchoolofChemistry,UniversityofNewSouthWales,Sydney,
Australia.
ProfessorDr.JohnGladysz,Institutfu¨rOrganischeChemie,Universita¨tErlangen-
Nu¨rnberg,Germany.
ProfessorPhilipParsons,SchoolofChemistry,PhysicsandEnvironmentalSci-
ence,UniversityofSussex,UK.
ProfessorPeterStang,DepartmentofChemistry,UniversityofUtah,Utah,USA.
TitlesintheSeries
ProtectingGroupsinOrganicSynthesis
JamesR.Hanson
OrganicSynthesiswithCarbohydrates
Geert-JanBoonsandKarlJ.Hale
OrganicSynthesisusingTransitionMetals
RoderickBates
StoichiometricAsymmetricSynthesis
MarkRizzacasaandMichaelPerkins
CatalysisinAsymmetricSynthesis(SecondEdition)
VittorioCaprioandJonathanM.J.Williams
ReactionMechanismsinOrganicSynthesis
RakeshKumarParashar
Forthcoming
PhotochemistryofOrganicCompounds:FromConceptstoPractice
PetrKla´nandJakobWirz
PracticalBiotransformations
GideonGrogan
ii
P1:SFK/XXX P2:SFK/XXX QC:SFK/XXX T1:SFK
fm JWBK273-Caprio November25,2008 9:49 Printer:Yettocome
Catalysis in Asymmetric Synthesis
Second Edition
Vittorio Caprio
DepartmentofChemistry
UniversityofAuckland,Auckland,NewZealand
and
Jonathan M. J. Williams
DepartmentofChemistry
UniversityofBath,Bath,UK
A John Wiley and Sons, Ltd., Publication
iii
P1:SFK/XXX P2:SFK/XXX QC:SFK/XXX T1:SFK
fm JWBK273-Caprio November25,2008 9:49 Printer:Yettocome
Thiseditionfirstpublished2009
(cid:1)C VittorioCaprioandJonathanM.J.Williams
Thistextisbasedon“CatalysisinAsymmetricSynthesis”byJonathanM.J.Williams,publishedby
SheffieldAcademicPressin1999andacquiredbyBlackwellPublishingin2002.
BlackwellPublishingwasacquiredbyJohnWiley&SonsinFebruary2007.Blackwell’spublishing
programmehasbeenmergedwithWiley’sglobalScientific,Technical,andMedicalbusinesstoform
Wiley-Blackwell.
Registeredoffice
John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ,
UnitedKingdom
Editorialoffices
9600GarsingtonRoad,Oxford,OX42DQ,UnitedKingdom
2121StateAvenue,Ames,Iowa50014-8300,USA
For details of our global editorial offices, for customer services and for information about how
to apply for permission to reuse the copyright material in this book please see our website at
www.w ile y.com/w ile y-blackwe ll.
Therightoftheauthortobeidentifiedastheauthorofthisworkhasbeenassertedinaccordancewith
theCopyright,DesignsandPatentsAct1988.
All rights reserved. No part of this publication may be reproduced, stored in a retrieval system,
or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or
otherwise,exceptaspermittedbytheUKCopyright,DesignsandPatentsAct1988,withouttheprior
permissionofthepublisher.
Wileyalsopublishesitsbooksinavarietyofelectronicformats.Somecontentthatappearsinprint
maynotbeavailableinelectronicbooks.
Designationsusedbycompaniestodistinguishtheirproductsareoftenclaimedastrademarks.All
brandnamesandproductnamesusedinthisbookaretradenames,servicemarks,trademarksor
registeredtrademarksoftheirrespectiveowners.Thepublisherisnotassociatedwithanyproductor
vendormentionedinthisbook.Thispublicationisdesignedtoprovideaccurateandauthoritative
informationinregardtothesubjectmattercovered.Itissoldontheunderstandingthatthepublisher
isnotengagedinrenderingprofessionalservices.Ifprofessionaladviceorotherexpertassistanceis
required,theservicesofacompetentprofessionalshouldbesought.
LibraryofCongressCataloging-in-PublicationData
Caprio,Vittorio.
Catalysisinasymmetricsynthesis/VittorioCaprioandJonathanM.J.Williams.–2nded.
p. cm.
Includesbibliographicalreferencesandindex.
ISBN978-1-4051-9091-6(cloth)–ISBN978-1-4051-7519-7(pbk.:alk.paper)
1.Asymmetricsynthesis. 2.Catalysis. I.Williams,JonathanM.J. II.Title.
QD262.C282008
541(cid:2).39–dc22 2008045023
AcataloguerecordforthisbookisavailablefromtheBritishLibrary.
Setin10/12ptMinionbyAptaraInc.,NewDelhi,India
PrintedandboundinGreatBritainbyTJInternational,Ltd,Padstow,Cornwall
1 2008
iv
P1:SFK/XXX P2:SFK/XXX QC:SFK/XXX T1:SFK
fm JWBK273-Caprio November25,2008 9:49 Printer:Yettocome
ToJenny
v
P1:SFK/XXX P2:SFK/XXX QC:SFK/XXX T1:SFK
fm JWBK273-Caprio November25,2008 9:49 Printer:Yettocome
vi
P1:SFK/XXX P2:SFK/XXX QC:SFK/XXX T1:SFK
fm JWBK273-Caprio November25,2008 9:49 Printer:Yettocome
Contents
PrefacetotheSecondEdition xi
PrefacetotheFirstEdition xiii
1 Introduction 1
1.1 ReactionsAmenabletoAsymmetricCatalysis 1
1.2 Assignmentof(R)and(S)StereochemicalDescriptors 2
FutherReading 6
References 7
2 ReductionofAlkenes 9
2.1 AsymmetricHydrogenationwithRhodiumComplexes 9
2.2 AsymmetricHydrogenationwithRutheniumCatalysts 18
2.3 AlkeneHydrogenationwithTitaniumand
ZirconiumCatalysts 24
2.4 AlkeneHydrogenationwithIridiumCatalysts 25
2.5 AlkeneHydrogenationwithOrganocatalysts 28
2.6 AlkeneHydrosilylation 29
2.7 AlkeneHydroboration 32
2.8 Hydroamination 34
2.9 Hydroformylation 36
2.10 HydroacylationofAlkenes 39
2.11 HydrocyanationofAlkenes 40
References 40
3 ReductionofKetonesandImines 47
3.1 HydrogenationofKetones 47
3.2 HydrogenationandTransferHydrogenationofImines
andRelatedCompounds 53
3.3 TransferHydrogenationofKetones 56
3.4 HeterogeneousHydrogenation 59
3.5 ReductionofKetonesUsingEnantioselective
BorohydrideReagents 63
3.6 HydrosilylationofKetones 68
3.7 HydrosilylationofIminesandNitrones 73
References 75
vii
P1:SFK/XXX P2:SFK/XXX QC:SFK/XXX T1:SFK
fm JWBK273-Caprio November25,2008 9:49 Printer:Yettocome
viii Contents
4 Epoxidation 81
4.1 EpoxidationofAllylicAlcohols 81
4.2 EpoxidationwithMetal(salen)Complexes 88
4.3 EpoxidationUsingMetal–Porphyrin-BasedCatalysts 94
4.4 OtherMetal-CatalysedEpoxidationsof
UnfunctionalisedOlefins 95
4.5 EpoxidationofElectron-DeficientAlkenes 96
4.6 EpoxidationwithIminiumSalts 101
4.7 EpoxidationwithKetoneCatalysts 102
4.8 EpoxidationofAldehydes 105
4.9 AziridinationofAlkenes 106
4.10 AziridinationofImines 108
References 109
5 FurtherOxidationReactions 117
5.1 Dihydroxylation 117
5.2 Aminohydroxylation 126
5.3 α-HeterofunctionalisationofAldehydesandKetones 130
5.4 OxidationofC–H 136
5.5 Baeyer–VilligerOxidation 138
5.6 OxidationofSulfides 139
References 142
6 NucleophilicAdditiontoCarbonylCompounds 147
6.1 AdditionofOrganozincstoCarbonylCompounds 147
6.2 AdditionofCyanidetoAldehydesandKetones 153
6.3 AllylationofAldehydes 160
6.4 HydrophosphonylationofAldehydes 165
6.5 NucleophilicAdditionstoImines 166
References 173
7 TheAldolandRelatedReactions 179
7.1 TheAldolReaction 180
7.2 IsocyanideandRelatedAldolReactions 191
7.3 TheNitroaldolReaction 193
7.4 AdditionofEnolatestoImines 195
7.5 DarzensCondensation 200
7.6 Morita–Baylis–HillmanReaction 201
7.7 Carbonyl-EneReactions 203
References 208
8 Cycloadditions 213
8.1 Diels–AlderReactions 213
8.2 InverseElectronDemandDiels–AlderReactions 231
P1:SFK/XXX P2:SFK/XXX QC:SFK/XXX T1:SFK
fm JWBK273-Caprio November25,2008 9:49 Printer:Yettocome
Contents ix
8.3 Hetero-Diels–AlderReactions 232
8.4 1,3-DipolarCycloadditionReactions 240
8.5 [2+2]Cycloadditions 246
8.6 Pauson–Khand-TypeReactions 249
References 251
9 CatalyticReactionsInvolvingCarbenesandYlides 257
9.1 Cyclopropanation 257
9.2 InsertionReactions 268
9.3 AsymmetricYlideReactions 273
References 275
10 CatalyticCarbon–CarbonBond-FormingReactions 281
10.1 Cross-CouplingReactions 282
10.2 Metal-CatalysedAllylicSubstitution 284
10.3 HeckReactions 296
10.4 AlkylmetalationofAlkenes 302
References 305
11 ConjugateAdditionReactions 311
11.1 ConjugateAdditionofEnolates 311
11.2 ConjugateAdditionofSulfurNucleophiles 317
11.3 ConjugateAdditionofNonstabilisedNucleophiles 320
11.4 ConjugateAdditionwithNitrogen-BasedNucleophiles
andElectrophiles 325
References 328
12 FurtherCatalyticReactions 333
12.1 IsomerisationsandRearrangements 333
12.2 DeprotonationReactions 336
12.3 ProtonationReactions 336
12.4 AlkylationandAllylationofEnolates 338
12.5 FormationofAlkenes 342
12.6 Oxyselenylation-EliminationReactions 344
12.7 TheBenzoinCondensation 344
12.8 EsterFormationandHydrolysis 345
12.9 Ring-OpeningofEpoxides 349
References 355
Index 361