Rh-Catalyzed Asymmetric Arylative Cyclization of Alkyne-Tethered Aliphatic Ketones: Access to Enantioenriched Heterocyclic Tertiary Allylic Alcohols.

By employing a simple and readily available chiral difluorphos ligand, a highly enantioselective rhodium-catalyzed asymmetric arylation tandem cyclization of heteroatom-containing alkyne-tethered aliphatic ketones with boronic acids was achieved under mild conditions. This protocol offers efficient and practical access to a broad spectrum of chiral heterocyclic tertiary allylic alcohols bearing trisubstituted or tetrasubstituted alkene functionality in good yields (up to 86%) with excellent enantioselectivities (up to 99% ee). Moreover, the synthetic utility of this methodology has been demonstrated via the rapid and concise construction of various structurally intriguing chiral heterocyclic architectures.