Stereodefined Skipped Dienes through Iridium‐Catalyzed Formal Addition of Tertiary Allylic C−H Bonds to Alkynes

Abstract Preparation of skipped dienes with a quaternary carbon center at the C‐3 position remains a synthetic challenge. We report here an iridium‐catalyzed formal addition of tertiary sp 3 C−H bond to alkyne for the facile preparation of skipped dienes. The tertiary allylic C−H bond is cleaved regioselectively, at the site of which a new C−C bond is formed. Enantioselective construction of acyclic quaternary carbon stereocenters is also demonstrated.