LAUSR

Alkene dicarbofunctionalizations represent streamline the construction of aliphatic structures and have thus been the subject of intense research efforts. Despite significant progress, catalytic asymmetric variants remain scarce. Inspired by the advantages of reductive cross-coupling approaches, we present here a highly efficient asymmetric intermolecular Ni-catalyzed reductive dicarbo-functionalization of alkenes. Two distinct readily available electrophiles, namely Csp2- and Csp3- halides are added simultaneously across a variety of olefins (vinyl amides, vinyl boranes, vinyl phosphates) at room temperature in a highly regio- and enantioselec-tive manner. The reaction, devoid of sensitive of organometallic reagents, takes advantage of an in situ generated chiral alkyl Ni(III)-intermediate to ensure a stereodefined outcome in the Csp3-Csp2 bond forming reaction. An (L)-(+)-isoleucine chiral bi-soxazoline ligand and the presence of coordinating sites on the alkene are key for the successful outcome in these "Asymmetric Radical Relayed Reductive Coupling" (ARRRC). Further, multiple transformations of the chiral amides obtained in this process showcase the potential of this new methodology for the straightforward assembly of chiral building blocks such as primary and secondary amines, oxazolines, etc. highlighting its synthetic utility.