Chiral Sulfur Ligands: Asymmetric Catalysis (RSC Catalysis Series)

402 Pages·2009·2.994 MB·English

by  Hélène Pellissier

Chiral Sulfur Ligands
Asymmetric Catalysis
RSC Catalysis Series
Series Editor:
ProfessorJamesJSpivey,LouisianaStateUniversity,BatonRouge,USA
Advisory Board:
KrijnPdeJong,UniversityofUtrecht,TheNetherlands,JamesADumesic,Universityof
Wisconsin-Madison,USA,ChrisHardacre,Queen’sUniversityBelfast,NorthernIreland,
Enrique Iglesia, University of California at Berkeley, USA, Zinfer Ismagilov, Boreskov
Institute of Catalysis, Novosibirsk, Russia, Johannes Lercher, TU Mu¨nchen, Germany,
UmitOzkan,OhioStateUniversity,USA,ChunshanSong,PennStateUniversity,USA
Titles in the Series:
1:CarbonsandCarbonSupportedCatalystsinHydroprocessing
2:ChiralSulfurLigands:AsymmetricCatalysis
How to obtain future titles on publication:
Astandingorderplanisavailableforthisseries.Astandingorderwillbringdeliveryof
eachnewvolumeimmediatelyonpublication.
For further information please contact:
Sales and Customer Care, Royal Society of Chemistry, Thomas Graham
House, Science Park, Milton Road, Cambridge, CB4 0WF, UK
Telephone:[phone],Fax:[phone],Email:[email protected]
Visit our websiteathttp://www.rsc.org/Shop/Books/
Chiral Sulfur Ligands
Asymmetric Catalysis
He´le`ne Pellissier
CNRS and Paul Ce´zanne University Aix-Marseille III, Institute of Molecular
Sciences, Marseille, France
RSCCatalysisSeriesNo.2
ISBN: 978-1-84755-924-1
ISSN: 1757-6725
AcataloguerecordforthisbookisavailablefromtheBritishLibrary
rHe´le`nePellissier2009
Allrightsreserved
Apartfromfairdealingforthepurposesofresearchfornon-commercialpurposesor
forprivatestudy,criticismorreview,aspermittedundertheCopyright,Designsand
PatentsAct1988andtheCopyrightandRelatedRightsRegulations2003,thispublication
maynotbereproduced,storedortransmitted,inanyformorbyanymeans,withoutthe
priorpermissioninwritingofTheRoyalSocietyofChemistryorthecopyrightowner,or
inthecaseofreproductioninaccordancewiththetermsoflicencesissuedbythe
CopyrightLicensingAgencyintheUK,orinaccordancewiththetermsofthelicences
issuedbytheappropriateReproductionRightsOrganizationoutsidetheUK.Enquiries
concerningreproductionoutsidethetermsstatedhereshouldbesenttoTheRoyalSociety
ofChemistryattheaddressprintedonthispage.
PublishedbyTheRoyalSocietyofChemistry,
ThomasGrahamHouse,SciencePark,MiltonRoad,
CambridgeCB40WF,UK
RegisteredCharityNumber207890
Forfurtherinformationseeourwebsiteatwww.rsc.org
In loving memory of Cyril and Vale´rie Pellissier
Dedicated to their so little children, Tess and Cle´ment

Preface
The preparation of chiral compounds is an important and challenging area
of contemporary synthetic organic chemistry, mainly in connection with the
fact that most natural products are chiral and their physiological or pharma-
cological properties depend upon their recognition by chiral receptors, which
will interact only with molecules of the proper absolute configuration. The
use of chiral drugs in enantiopure form is now a standard requirement for
virtually every new chemical entity, and the development of new synthetic
methods to obtain enantiopure compounds has become a key goal for phar-
maceutical companies. Indeed, the growing economic importance of chiral
compounds has spurred major research efforts towards the selective prepara-
tion of chiral compounds. The synthesis of optically active chiral com-
pounds, which play an important role in medicine and materials, is one of
the most fascinating aspects of modern organic synthesis. Over the last three
decades an explosive growth of research in the field of asymmetric synthesis
has occurred. Asymmetric synthesis constitutes one of the main strategies to
gain access to enantioenriched compounds, involving the use of either chiral
auxiliaries or catalysts derived preferentially from cheap chiral pool sources.
In particular, asymmetric catalysis of organic reactions to provide enantio-
merically enriched products is of central importance to modern synthetic and
pharmaceutical chemistry.
In this context, the development of chiral ligands for asymmetric catalytic
reactions is a subject of considerable interest in the field of asymmetric
synthesis. Extensive efforts have been made for the development of new
advantageouschiralligandsapplicableinabroadvarietyofreactiontypesand
their preparation continues to be an important area of synthetic organic
research. Indeed, the ligand design is becoming an increasingly important
part of the synthetic activity in chemistry. This is, of course, because of
the subtle control that ligands exert on the metal centre to which they are
coordinated. The impressive number of reports dealing with the use of chiral
RSCCatalysisSeriesNo.2
ChiralSulfurLigands:AsymmetricCatalysis
ByHe´le`nePellissier
rHe´le`nePellissier2009
PublishedbytheRoyalSocietyofChemistry,www.rsc.org
vii
viii Preface
sulfur-containing ligands for asymmetric catalysis is well representative of the
success of such ligands to promote numerous catalytic transformations.
Nowadays, these ligands have become fairly renowned competitors to more
usual phosphorus- or nitrogen-containing ligands. Indeed, chiral sulfur-con-
tainingligandsrepresentahighlyefficientclassofligandsapplicableinabroad
variety of reaction types, also in view of some peculiar properties, which dif-
ferentiate them from more popular ligands such as phosphorus- or nitrogen-
containing ligands. In particular, the stereoelectronic assistance of organo-
sulfur functionalities and the possibility of stereocontrol through stereogenic
sulfur atoms can provide interesting results in many applications. The key
advantages of these new types of ligands are their easy synthesis, mostly
startingfromreadilyavailablecommercialcompounds,andtheirhighstability,
which allows easy storage and handling, especially compared to phosphine
derivatives. Whereas the synthesis of chiral phosphorus ligands is often com-
plex and difficult, the preparation of chiral sulfur compounds is much more
convenient. Consequently, a wide diversity of chiral sulfur-containing ligands,
more than forty different classes, is easily available either directly from the
chiral pool or by facile modifications of other heteroatomic ligands. Many of
thesulfur-containingligandshaveonlyrecentlyappearedintheliterature,and
it is clear that their application in asymmetric catalysis will undoubtedly
increaseinthenearfutureforanumberofadditionalasymmetricreactions,due
in part to their easy synthesis. Moreover, due to their great stability, asym-
metricheterogeneouscatalysisseemstobeagoodwaytodevelopthepotential
of these ligands in an economic and environmentally friendly manner.
The goal of this book is to provide to researchers and professionals of aca-
demicandindustriallaboratoriesabroadoverviewoftheworksconcerningthe
useofchiralsulfur-containingligandsinoneofthemostimportantfocalareas
inorganicsynthesis,asymmetriccatalysis.Thebookisdividedintotenchapters
correspondingtothedifferenttypesofreactionsbasedontheuseofcomplexes
containingchiralsulfurligands,suchasallylicsubstitution,conjugateaddition,
addition of organometallic reagents to aldehydes, addition of organozinc
reagents to ketones, Diels–Alder reaction, cyclopropanation, Heck-type reac-
tions, hydrogenation, hydrogen transfer and miscellaneous reactions.
Contents
General Introduction 1
Chapter 1 Allylic Substitution 7
1.1 Introduction 7
1.2 S/S Ligands 10
1.3 S/P Ligands 15
1.4 S/N Ligands 26
1.5 S/C and S/O Ligands 40
1.6 Sulfur-Containing P/N, P/O, N/N, N/O and
P/P Ligands 41
1.7 Sulfur-Containing Ferrocenyl Ligands 53
1.8 Conclusions 64
References 65
Chapter 2 Conjugate Addition 74
2.1 Introduction 74
2.2 Copper Catalysts 75
2.3 Other Metal Catalysts 96
2.4 Conclusions 101
References 101
Chapter 3 Addition of Organometallic Reagents to Aldehydes 105
3.1 Introduction 105
3.2 Addition of Organozinc Reagents to Aldehydes 106
RSCCatalysisSeriesNo.2
ChiralSulfurLigands:AsymmetricCatalysis
ByHe´le`nePellissier
rHe´le`nePellissier2009
PublishedbytheRoyalSocietyofChemistry,www.rsc.org
ix
x Contents
3.2.1 Addition of Dialkylzinc Reagents to
Aldehydes 106
3.2.1.1 S/N Ligands 106
3.2.1.2 S/N/O Ligands 119
3.2.1.3 S/O Ligands 138
3.2.1.4 Sulfur-Containing Ferrocenyl
Ligands 141
3.2.2 Addition of Aryl-, Alkenyl- and Alkynylzinc
Reagents to Aldehydes 142
3.3 Addition of Organometallic Reagents other than
Organozinc Reagents 147
3.4 Conclusions 150
References 150
Chapter 4 Addition of Organozinc Reagents to Ketones 156
References 181
Chapter 5 Diels–Alder Reaction 184
References 205
Chapter 6 Cyclopropanation 208
6.1 Introduction 208
6.2 Transition-Metal-Catalysed Decomposition of
Diazoalkanes 209
6.2.1 Sulfide Ligands 210
6.2.2 Thiophene Ligands 210
6.2.3 Sulfoxide Ligands 214
6.2.4 Sulfonamide Ligands 214
6.3 Simmons–Smith Cyclopropanation 222
6.4 Conclusions 228
References 229
Chapter 7 Heck-Type Reactions 233
References 241
Chapter 8 Hydrogenation 243
8.1 Introduction 243
8.2 Hydrogenation of Olefins 243
8.3 Hydrogenation of Ketones 259
8.4 Conclusions 267
References 268