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 RhI–OH complex, enables the conjugate transfer of nucleophilic silicon onto α,β-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.