Enantioselective Pd- and Cu-Catalyzed Hydrofunctionalization of Methylenecyclopropanes via a Distal C-C Bond Cleavage.

The enantioselective ring-opening reactions of methylenecyclopropanes (MCPs) involving C-C bond activation via oxidative addition of transition metals have been rarely reported. Here, we disclose a Pd/Cu-catalyzed enantio- and regioselective coupling between cyclic imino esters and MCPs to produce α-allylated 2-pyrrole derivatives. In this reaction, azomethine ylide formed by a chiral copper catalyst with ketimine ester would serve as a nucleophile to react with activated MCPs via palladium catalysis. This bimetallic catalyst system exhibited a broad substrate scope and high regio- and enantioselectivities.