Enantioselective [3 + 2] Cycloaddition Reaction of Ethynylethylene Carbonates with Malononitrile Enabled by Organo/Metal Cooperative Catalysis

Abstract

The first catalytic asymmetric decarboxylative [3 + 2] cycloaddition reaction of ethynylethylene carbonates with malononitrile has been developed successfully by an organo/copper cooperative system. This strategy led to a series of optically active polysubstituted dihydrofurans in good yields with high levels of enantioselectivities (up to 99% yield, 97% ee). The presence of the terminal alkynyl and the cyano group in the dihydrofuran products provides a wide scope for further structural transformations. More importantly, this organo/metal cooperative catalytic system will broaden the substrate scope and enable fundamentally new reactions.