A practical concept for catalytic carbonylations using carbon dioxide

The rise of CO₂ in atmosphere is considered as the major reason for global warming. Therefore, CO₂ utilization has attracted more and more attention. Among those, using CO₂ as C1-feedstock for the chemical industry provides a solution. Here we show a two-step cascade process to perform catalytic carbonylations of olefins, alkynes, and aryl halides utilizing CO₂ and H₂. For the first step, a novel heterogeneous copper 10Cu@SiO₂-PHM catalyst exhibits high selectivity (≥98%) and decent conversion (27%) in generating CO from reducing CO₂ with H₂. The generated CO is directly utilized without further purification in industrially important carbonylation reactions: hydroformylation, alkoxycarbonylation, and aminocarbonylation. Notably, various aldehydes, (unsaturated) esters and amides are obtained in high yields and chemo-/regio-selectivities at low temperature under ambient pressure. Our approach is of interest for continuous syntheses in drug discovery and organic synthesis to produce building blocks on reasonable scale utilizing CO₂.