Rhodium‐Complex‐Catalyzed Hydroformylation of Olefins with CO 2 and Hydrosilane

A rhodium‐catalyzed one‐pot hydroformylation of olefins with CO 2  , 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 CO 2 reduction to CO and a conventional rhodium‐catalyzed hydroformylation with CO/H 2 . The hydrosilylane‐mediated reduction of CO 2 in preference to aldehydes was found to be crucial for the selective formation of aldehydes under the reaction conditions.