Boehm Philip, Roediger Sven, Bismuto Alessandro, Morandi Bill
Laboratorium für Organische Chemie, ETH Zürich, Vladimir-Prelog-Weg 3, HCI, 8093, Zürich, Switzerland.
Angew Chem Int Ed Engl. 2020 Oct 5;59(41):17887-17896. doi: 10.1002/anie.202005891. Epub 2020 Aug 13.
An efficient palladium-catalyzed chlorocarbonylation of aryl (pseudo)halides that gives access to a wide range of carboxylic acid derivatives has been developed. The use of butyryl chloride as a combined CO and Cl source eludes the need for toxic, gaseous carbon monoxide, thus facilitating the synthesis of high-value products from readily available aryl (pseudo)halides. The combination of palladium(0), Xantphos, and an amine base is essential to promote this broadly applicable catalytic reaction. Overall, this reaction provides access to a great variety of carbonyl-containing products through in situ transformation of the generated aroyl chloride. Combined experimental and computational studies support a reaction mechanism involving in situ generation of CO.
已开发出一种高效的钯催化芳基（拟）卤化物的氯羰基化反应，该反应可用于制备多种羧酸衍生物。使用丁酰氯作为一氧化碳和氯的组合来源，无需使用有毒的气态一氧化碳，从而便于从易得的芳基（拟）卤化物合成高价值产品。钯（0）、Xantphos和胺碱的组合对于促进这种广泛适用的催化反应至关重要。总体而言，该反应通过原位转化生成的芳酰氯，可制备多种含羰基的产物。实验和计算研究相结合支持了一种涉及一氧化碳原位生成的反应机理。
