Desymmetrization of 1,4‐Diynes by Allylic Alcohol‐Triggered Redox Enyne Cycloisomerization

Abstract We report herein an unprecedented desymmetrization of 1,4‐diynes via a Rh‐catalyzed asymmetric redox cycloisomerization. This method adopts allylic alcohol‐containing diynes and provides efficient access to multi‐functional pyrrolidines and tetrahydrofurans in high to excellent stereoselectivities. Mechanistic studies highlighted an innovative catalytic pathway that differs from the classical enyne cycloisomerization and involves initiation at the allylic alcohol moiety. Diverse derivatizations of the heterocyclic products including intriguing skeletal rearrangements have also been demonstrated.