Abstract:The construction of multi-stereocenters of transition metal-catalyzed cross-coupling reaction is a stubborn challenge. In the meanwhile, catalytic desymmetric functionalization of unactivated alkene remains largely unexplored.Herein,we disclose an unprecedented desymmetric dicarbofunctionalization of 1,6-dienes via nickel-catalyzed reductive cross-coupling reaction. The leverage of underdeveloped chiral 8-Quinox enables Ni-catalyzed desymmetric carbamoylalkylation of both unactivated mono- and disubstituted alkenes to forge the pyrrolidinone bearing two uncontinuous stereogenic centers in high enantio- and stereoselectivitives with broad funcitional group tolerance .The synthetic application of pyrrolidinones allows the rapid access to the complex chiral fused-heterocycles.