Chemistry Reference
In-Depth Information
9
ASYMMETRIC HYDROSILYLATION OF
CARBON - CARBON DOUBLE BONDS
AND RELATED REACTIONS
JIN WOOK HAN
Department of Chemistry, College of Natural Sciences, Hanyang University,
Seoul 133 - 791, Korea
TAMIO HAYASHI
Department of Chemistry, Faculty of Science, Kyoto University, Sakyo-ku,
Kyoto 606 - 8502, Japan
9.1. INTRODUCTION
Asymmetric hydrometallation of unsaturated substrates catalyzed by chiral transition
metal complexes and a subsequent transformation of the hydrometallated compound
provide an effi cient asymmetric heterofunctionalization [1]. Transition metal-catalyzed
asymmetric hydrosilylation and hydroboration of carbon-carbon unsaturated com-
pounds followed by the oxidative cleavage of the resulting C-Si and C-B bonds give
enantiomerically enriched alcohols (Scheme 9.1 ).
In this chapter, recent advances in asymmetric hydrosilylation and related hydro-
metallation reactions catalyzed by chiral transition metal complexes will be reviewed
according to the reaction substrates. Not only effi cient catalytic systems with various
transition metals and chiral ligands in order to achieve good catalytic activities and
enantioselelctivities have been developed extensively but also the reaction scopes of
substrates have been broadened to shed a light on new utilizations of asymmetric hydro-
silylation during the last decade. Asymmetric hydrosilylation of olefi ns has been extended
to palladium-catalyzed hydrosilylation of 1,3-enynes, giving optically active allenylsi-
lanes and rhodium-catalyzed intramolecular cyclization/hydrosilylation of 1,6-dienes and
1,6-enynes giving a cyclic hydrosilylated product. This chapter also discusses transition
