| Abstract: | A rhodium‐catalyzed one‐pot hydroformylation of olefins with CO2 , hydrosilane, and H2 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/H2. 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. |
