Abstract

Heterolytic cleavage of the Si–B bond through transmetalationwith (chiral) Cu–O or Rh–O complexes produces syntheticallyuseful silicon nucleophiles that participate in several typicalC–Si bond-forming reactions. Conjugate addition proceedswith superb levels of enantiocontrol employing either Cu(I)–carbene or Rh(I)–phosphine complexes, and an asymmetriciminium ion catalysis merged with an achiral Cu(I)-catalysedSi–B bond activation is now also known. The Cu(I) catalysis isan attractive alternative entry into the established chemistryof silicon-based cuprates and displays considerable scope,as further exemplified by regioselective allylic substitutionand addition reactions.