Recent advances in copper-catalyzed asymmetric propargylic substitution

Copper-catalyzed enantioselective propargylic substitution has become an increasingly reliable strategy to construct stereogenic centers over the past two decades. Currently, various catalytic systems and reaction modes have been developed for the synthesis of different chiral propargylic frameworks. Therein, stereochemical control can be achieved either through the nucleophilic addition at the γ-site of the copper-allenylidene intermediate, or the newly proposed nucleophilic addition of copper-vinylvinylidene intermediate comprising two reactive sites (γ, ε). This review briefly summarizes the development of copper-catalyzed asymmetric propargylic substitution on a variety of different substrates, including but not limited to propargylic esters, cyclic carbonates and carbamates, and yne-allylic esters.