Cu-Catalyzed Selective 1,5-Hydrophosphoro(di)thiolation of Vinyl Cyclopropanes

Herein, we report a copper-catalyzed selective 1,5-hydrophosphoro(di)thiolation of vinylcyclopropanes with various S-hydrogen phosphor(di)thioates without the need for a supported ligand. This protocol provides an efficient method for the preparation of structurally diverse homoallylic phosphorodithioates, featuring broad substrate scope and excellent regio- and stereoselectivity. Mechanistic investigations, including DFT calculations and XPS analysis, suggest that the CuBr catalyst acts as a Lewis acid, activating the S-hydrogen phosphorthioates via coordination reaction and promoting this transformation.