Nickel-Catalyzed Electronically Reversed Enantioselective Hydrocarbofunctionalizations of Acrylamides

Asymmetric hydrocarbofunctionalization of alkenes has emerged as an efficient strategy for synthesizing optically active molecules through a carbon-carbon bond-forming process from readily available alkenes and carboelectrophiles. Here, we present a summary of our efforts to control the regio- and enantioselectivity of hydrocarbofunctionalizations of electron-deficient alkenes with a nickel catalyst and a chiral bisoxazolidine ligand. The reaction permits electron-reversed hydrocarbofunctionalizations of acrylamides with excellent enantioselectivity. This operationally simple protocol permits the asymmetric hydroalkylation, hydrobenzylation, or hydropropargylation of acrylamides. This reaction is useful for preparing a wide range of α-branched chiral amides with broad functional-group tolerance.