Nickel-catalyzed enantioselective reductive carbo-acylation of alkenes

Abstract

Recently, transition-metal-catalyzed asymmetric dicarbofunctionalization of tethered alkenes has emerged as a powerful method for construction of chiral cyclic carbo- and heterocycles. However, all these reactions rely on facially selective arylmetalation of the pendant olefinic unit. Here, we successfully apply acylnickelation as the enantiodetermining step in the asymmetric nickel-catalyzed reductive carbo-acylation of aryl carbamic chloride-tethered alkenes with primary and secondary alkyl iodides as well as benzyl chlorides as the coupling partners, using manganese as a reducing agent. By circumventing the use of pre-generated organometallics, this reductive strategy enables the synthesis of diverse enantioenriched oxindoles bearing a quaternary stereogenic center under mild reaction conditions with high tolerance of a broad range of functional moieties.