A practical concept for catalytic carbonylations using carbon dioxide.

The rise of CO 2 in atmosphere is considered as the major reason for global warming. Therefore, CO 2 utilization has attracted more and more attention. Among those, using CO 2 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 2 and H 2 . For the first step, a novel heterogeneous copper 10Cu@SiO 2 -PHM catalyst exhibits high selectivity (≥98%) and decent conversion (27%) in generating CO from reducing CO 2 with H 2 . 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 2 .