Enantioselective Metal-Catalyzed Reductive Coupling of Alkynes with Carbonyl Compounds and Imines: Convergent Construction of Allylic Alcohols and Amines

The use of alkynes as vinylmetal pronucleophiles in intermolecular enantioselective metal-catalyzed carbonyl and imine reductive couplings to form allylic alcohols and amines is surveyed. Related hydrogen auto-transfer processes, wherein alcohols or amines serve dually as reductants and carbonyl or imine proelectrophiles, also are cataloged, as are applications in target-oriented synthesis. These processes represent an emerging alternative to the use of stoichiometric vinylmetal reagents or Nozaki-Hiyama-Kishi (NHK) reactions in carbonyl and imine alkenylation.