Copper-Catalyzed Asymmetric Cloke–Wilson Rearrangement

Herein we describe the first transition-metal-catalyzed asymmetric Cloke-Wilson rearrangement through unprecedented propargylic alkenoxylation reaction with enol as the O-nucleophile. A set of new chiral PPBOX ligands was prepared to guarantee the high enantioselectivity of the transformation. A series of polysubstituted dihydrofuran skeletons bearing an alkyne unit was prepared in good yield and high enantioselectivity under very mild reaction conditions, and various downstream transformations were facilely conducted to access different chiral skeletons.