Sang Rui, Hu Yuya, Razzaq Rauf, Mollaert Guillaume, Atia Hanan, Bentrup Ursula, Sharif Muhammad, Neumann Helfried, Junge Henrik, Jackstell Ralf, Maes Bert U W, Beller Matthias
Leibniz-Institut für Katalyse e.V., Albert-Einstein-Str. 29a, 18059, Rostock, Germany.
Organic Synthesis Division, Department of Chemistry, University of Antwerp, Groenenborgerlaan 171, 2020, Antwerp, Belgium.
Nat Commun. 2022 Jul 30;13(1):4432. doi: 10.1038/s41467-022-32030-8.
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.
大气中一氧化碳（CO）含量的上升被认为是全球变暖的主要原因。因此，CO的利用越来越受到关注。其中，将CO用作化学工业的C1原料提供了一种解决方案。在此，我们展示了一种两步级联过程，用于利用CO和H对烯烃、炔烃和芳基卤化物进行催化羰基化反应。第一步，一种新型的非均相铜催化剂10Cu@SiO-PHM在利用H还原CO生成CO的过程中表现出高选择性（≥98%）和良好的转化率（27%）。所生成的CO无需进一步纯化即可直接用于重要的工业羰基化反应：氢甲酰化、烷氧羰基化和氨羰基化。值得注意的是，在常压低温下，各种醛、（不饱和）酯和酰胺能够以高产率以及化学/区域选择性获得。我们的方法对于药物发现和有机合成中的连续合成具有重要意义，能够利用CO合理规模地生产结构单元。
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