Rhodium(I)-catalyzed enantioselective 1,4-addition of nucleophilic silicon

A rhodium(I)-catalyzed activation of a silicon-boron linkage, that is, the transmetalation of silicon from boron to rhodium(I) by means of an Rh-1-OH complex, enables the conjugate transfer of nucleophilic silicon onto alpha,beta-unsaturated acceptors. Pre- or in situ formed cationic rhodium(I)-binap complexes catalyze this novel carbon-silicon bond formation with exceptional enantiocontrol, 92 to >99% ee for cyclic carbonyl and carboxyl Compounds as well as >99% ee for acyclic carboxyl compounds. (C) 2009 Elsevier Ltd. All rights reserved.