An Aza-Enolate Strategy Enables Iridium-Catalyzed Enantioselective Hydroalkenylations of Minimally Polarized Alkenes en Route to Complex N-Aryl β²-Amino Acids

Abstract

Cationic Ir­(I)-complexes modified with homochiral diphosphines promote the hydroalkenylative cross-coupling of β-(arylamino)­acrylates with monosubstituted styrenes and α-olefins. The processes are dependent on the presence of an NH unit, and it is postulated that metalation of this generates an iridium aza-enolate that engages the alkene during the C–C bond forming event. The method offers high branched selectivity and enantioselectivity and occurs with complete atom economy. Diastereocontrolled reduction of the products provides β2-amino acids that possess contiguous stereocenters.