Copper‐Catalyzed Asymmetric Borylative Cyclization of Cyclohexadienone‐Containing 1,6‐Dienes

Due to the low reactivity of 1,6‐dienes and the challenge of selectively differentiating such two olefins, the development of metal‐catalyzed asymmetric cyclization of 1,6‐dienes remains largely underdeveloped. Herein, we describe the first copper(I)‐catalyzed asymmetric borylative cyclization of cyclohexadienone‐tethered terminal alkenes (1,6‐dienes) via a tandem process: the regioselective borocupration of the electron‐rich terminal alkene and subsequent conjugate addition of stereospecific secondary alkyl‐copper(I) to the electron‐deficient cyclohexadienone, affording enantioenriched bicyclic skeletons bearing three contiguous stereocenters in all cis‐form. Meanwhile, this mild catalytic protocol is generally compatible with a wide range of functional groups, which allows further facile conversion of the cyclization products. magnified image