A practical concept for catalytic carbonylations using carbon dioxide.

Sang, Rui; Hu, Yuya; Razzaq, Rauf; Mollaert, Guillaume; Atia, Hanan; Bentrup, Ursula; Sharif, Muhammad; Neumann, Helfried et al. · Nat Commun · 2022

basic_science · Level V

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Abstract

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