A practical concept for catalytic carbonylations using carbon dioxide.

The rise of CO in atmosphere is considered as the major reason for global warming. Therefore, CO utilization has attracted more and more attention. Among those, using CO 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 CO and H. For the first step, a novel heterogeneous copper 10Cu@SiO-PHM catalyst exhibits high selectivity (≥98%) and decent conversion (27%) in generating CO from reducing CO with H. 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 CO.