Palladium‐Catalyzed Asymmetric Intramolecular Reductive Heck Desymmetrization of Cyclopentenes: Access to Chiral Bicyclo3.2.1octanes

A palladium-catalyzed asymmetric reductive Heck reaction of unactivated aliphatic alkenes, with eliminable β-hydrogen atoms, has been realized for the first time. A series of optically active bicyclo3.2.1octanes bearing chiral quaternary and tertiary carbon stereocenters were obtained in good yields with excellent enantioselectivities, exhibiting good functional-group tolerance and scalability. Moreover, deuterated optically active bicyclo3.2.1octanes were also obtained in high efficiency.