Luo Xiaoxue, Wang Yufeng, Wu Baijing, Wang Youdong, Li Cunpu, Shao Minhua, Liu Bin, Wei Zidong
State Key Laboratory of Advanced Chemical Power Sources, School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, China.
Department of Chemical and Biological Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong 999077, China.
J Phys Chem Lett. 2024 Oct 24;15(42):10435-10441. doi: 10.1021/acs.jpclett.4c02342. Epub 2024 Oct 10.
Baeyer-Villiger oxidation is a method with a 125-year history that produces lactones through a synergistic mechanism by reaction with stoichiometric peracids. Therefore, substituted lactones can be obtained from only substituted cyclic ketones. In this context, an electrochemical Baeyer-Villiger oxidation was developed using a CeO@PbO@Ti electrode, which produces substituted lactones through a stepwise mechanism. PbO, in combination with a benzoic acid molecular catalyst, can generate and utilize reactive oxygen species from electrochemical water splitting to serve as the oxidant. CeO is designed to promote the stepwise mechanism while suppressing the synergistic mechanism. Therefore, substituted lactone can be produced from unsubstituted cyclic ketone with high selectivity (77%) and yield (20 mM) through a carbocation rearrangement process. The developed stepwise electrochemical Baeyer-Villiger oxidation, using water as the oxygen source, offers a new green approach to organic synthesis.
拜耳-维立格氧化反应是一种有着125年历史的方法，它通过与化学计量的过酸反应，以协同机制生成内酯。因此，仅从取代的环酮就可以得到取代内酯。在此背景下，利用CeO@PbO@Ti电极开发了一种电化学拜耳-维立格氧化反应，该反应通过分步机制生成取代内酯。PbO与苯甲酸分子催化剂相结合，可以从电化学水分解中产生并利用活性氧作为氧化剂。CeO的设计目的是促进分步机制，同时抑制协同机制。因此，通过碳正离子重排过程，可以从未取代的环酮中以高选择性（77%）和高收率（20 mM）制备取代内酯。所开发的以水为氧源的分步电化学拜耳-维立格氧化反应为有机合成提供了一种新的绿色方法。
