Palladium/Rhodium Cooperative Catalysis for the Production of Aryl Aldehydes and Their Deuterated Analogues Using the Water–Gas Shift Reaction

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. Die reduktive Carbonylierung von Aryliodiden mit H2O als Hydridquelle und CO als Carbonylquelle und terminalem Reduktionsmittel gelang durch kooperative Pd/Rh‐Katalyse. Optimal für diese Synthese wertvoller Aldehyde sind der Ligand 4,4′‐Dimethoxy‐2,2′‐bipyridin und Tetramethylethylendiamin als Base.