A novel Pd/Rh dual‐metallic cooperative catalytic process has been developed to effect the reductive carbonylation of aryl halides in moderate to good yield. In this reaction, water is the hydride source, and CO serves both as the carbonyl source and the terminal reductant through the water–gas shift reaction. The catalytic generation of the Rh hydride allows for the selective formation of highly hindered aryl aldehydes that are inaccessible through previously reported reductive carbonylation protocols. Moreover, aldehydes with deuterated formyl groups can be efficiently and selectively synthesized using D₂O as a cost‐effective deuterium source without the need for presynthesizing the aldehyde.

中文翻译：

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钯/铑协同催化水-煤气变换反应生产芳醛及其氘代类似物

已开发出一种新颖的Pd / Rh双金属协同催化方法，以中等至良好的收率实现芳基卤化物的还原羰基化。在该反应中，水是氢化物源，CO通过水煤气变换反应既是羰基源，又是末端还原剂。Rh氢化物的催化生成可选择性形成受阻较高的芳基醛，而这些受阻芳基醛是以前报道的还原性羰基化方法无法达到的。此外，使用D ₂ O作为经济高效的氘源，可以高效且选择性地合成具有氘化甲酰基的醛，而无需预先合成醛。