Catalytic Enantioselective Synthesis of [alpha]-Substituted Secondary Allylic Alcohols from Terminal Alkynes and Aldehydes via Vinylaluminum Reagents

One-pot procedure: A general method for the highly enantioselective synthesis of α-substituted allylic alcohols has been developed starting from readily available terminal alkynes and aldehydes and proceeding via vinylaluminum reagents (see scheme, dppp=1,3-bis(diphenylphosphino)propane). The use of Me2 AlH is essential in the Ni-catalyzed hydroalumination step to generate vinylaluminum reagents that cannot reduce the aldehyde.