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

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.