Photoinduced Nickel-Catalyzed Enantioconvergent Synthesis of Allylic 1,3-Diols Bearing a Quaternary Stereocenter

Abstract An efficient and highly selective photoredox/nickel dual-catalytic strategy has been developed for the synthesis of chiral allylic 1,3-diols bearing fully substituted quaternary stereocenters from readily available vinyl cyclic carbonates (VCCs) and aldehydes. The transformation proceeds through in situ generation of nucleophilic allyl-Ni intermediates, enabling regio-, diastereo-, and enantioselective coupling with aldehydes to deliver the desired products in excellent yields and stereoselectivities. The protocol exhibits broad substrate scope, functional group tolerance, and scalability, providing versatile intermediates for downstream transformations without loss of stereochemical integrity. Mechanistic studies reveal that the reaction proceeds through a reductive quenching pathway and that a monomeric chiral Ni complex serves as the stereocontrol element. Collectively, these results address a long-standing challenge associated with the asymmetric construction of 1,3-diols bearing quaternary stereocenters.