Transition-Metal-Free Reductive Deoxygenative Olefination with CO2.

A new transition-metal-free reductive deoxygenative olefination of phosphorus ylides with CO2, an abundant and sustainable C1 chemical feedstock, is described. This catalytic CO2 fixation afforded β-unsubstituted acrylates and vinyl ketones in good yields with broad scope and good functional group tolerance under mild reaction conditions. Cost-effective and easily handled polymethylhydrosiloxane was used as a reductant. Bis(silyl)acetal was proved to be the key intermediate in this reductive functionalization of CO2.