Construction of Nonadjacent Stereocenters Through Iridium‐Catalyzed Desymmetric Hydroheteroarylation of Cyclopentenes

Abstract Transition metal–catalyzed direct addition of (hetero)aryl C─H bond to an alkene provides an expedited route to construct benzylic stereocenter from readily available arene and alkene feedstocks with complete atom‐economy. However, creation of more than one stereocenter through enantioselective C─H (hetero)arylation remains a challenging goal. Here we report an iridium‐catalyzed desymmetric hydroheteroarylation of cyclopentenes to construct 1,3‐nonadjacent stereocenters. A series of heteroaryl C─H bonds were cleaved site‐selectively and added regio‐ and enantioselectively to an unactivated alkene containing an amide coordinating group, delivering valuable enantioenriched cyclopentane scaffolds containing 1,3‐tertiary–tertiary or 1,3‐quaternary–tertiary stereocenters with exclusive diastereoselectivity and excellent enantioselectivity.