IRIDIUM-CATALYZED,ENANTIOSELECTIVE,ALLYLIC ALKYLATIONS WITH CARBON NUCLEOPHILES

摘要

We would like to thank the members of our groups for their numerous contributions to the development of the iridium-catalyzed allylic substitution reaction.Most of this work was supported by the Deutsche Forschungsgemeinschaft(Sonderforschungsbereich 623)and the Fonds der Chemischen Industrie.Thanks are due to Prof.Klaus Ditrich,BASF SE,for his generous donation of enantiopure arylalkylamines.We acknowledge the National Basic Research Program of China,NSFC,and the Chinese Academy of Sciences for generous financial support.We also thank Prof.Jin K.Cha and Prof.Scott E.Denmark for valuable suggestions,as well as Dr.Linda S.Press and Dr.Danielle Soenen for their patience and support during the preparation of this chapter.Metal-catalyzed allylic substitution(Tsuji-Trost reaction,Scheme 1)and its asymmetric variants have been in use for more than half a century.The great majority of these reactions involve palladium catalysis in combination with allylic substrates containing a leaving group Y,for example Y = OAc,and two identical terminal substituents(R~1 = R~2).1'2 However,other transition metals,such as molybdenum ruthenium,rhodium,and iridium,have recently attracted attention in asymmetric catalysis.Several reviews are available covering the whole range of metals.3,4