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 ...