NHC‐Ni(0) Catalyzed Diastereodivergent Hydroacylative Enyne Cyclization: Synthesis of Heterocycles bearing γ‐Enone

Abstract NHC‐Nickel(0) catalyzed 1,3‐ and 1,4‐diastereodivergent hydroacylative heteroenyne cyclization with aldehydes was achieved (Syn‐:Anti‐, switchable from up to 1:99 to 98:2). Both sets of heterocyclic diastereomers are accessible via this route, with a high γ‐:α‐enone structure ratio. Preliminary DFT investigations indicated that the manipulation of the N‐substituent exerts a direct influence on the diastereoselectivity of NHC‐nickelacyclopentene formation. The energy differences associated with the endocyclic bond angle (C−Z−C) changes noted in the calculations, might possibly account for the broad scope and high diastereodivergent selectivity observed. magnified image