Rhodium-Complex-Catalyzed Hydroformylation of Olefins with CO2 and Hydrosilane

A rhodium-catalyzed one-pot hydroformylation of olefins with CO2, hydrosilane, and H-2 has been developed that affords the aldehydes in good chemoselectivities at low catalyst loading. Mechanistic studies indicate that the transformation is likely to proceed through a tandem sequence of poly(methylhydrosiloxane) (PMHS) mediated CO2 reduction to CO and a conventional rhodium-catalyzed hydroformylation with CO/H-2. The hydrosilylane-mediated reduction of CO2 in preference to aldehydes was found to be crucial for the selective formation of aldehydes under the reaction conditions.