Hydroformylation of Olefins with CO2/H2 and Hydrosilane by Copper/Cobalt Tandem Catalysis

Abstract A Cu/Co tandem catalysis protocol was developed to conduct the hydroformylation of olefins using CO 2 /H 2 and PMHS (polymethylhydrosiloxane) as a readily available and environmentally friendly hydride source. This methodology was performed via a two‐step approach consisting of the copper‐catalyzed reduction of CO 2 by hydrosilane and subsequent cobalt‐promoted hydroformylation with H 2 and the in situ formed CO. The optimized triphos oxide ligand, which presumably facilitates the migratory insertion of CO gives moderate to excellent yields for both terminal and internal alkenes. This earth‐abundant metal catalysis provides a reliable and efficient way to afford useful aldehydes in industry using silicon by‐product PMHS as hydrogen source and renewable CO 2 as carbonyl source.