{"title":"以水为氧源的逐步电化学拜尔-维利格氧化法","authors":"Xiaoxue Luo, Yufeng Wang, Baijing Wu, Youdong Wang, Cunpu Li, Minhua Shao, Bin Liu, Zidong Wei","doi":"10.1021/acs.jpclett.4c02342","DOIUrl":null,"url":null,"abstract":"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<sub>2</sub>@PbO<sub>2</sub>@Ti electrode, which produces substituted lactones through a stepwise mechanism. PbO<sub>2</sub>, 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<sub>2</sub> 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.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":4.8000,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"A Stepwise Electrochemical Baeyer–Villiger Oxidation with Water as the Oxygen Source\",\"authors\":\"Xiaoxue Luo, Yufeng Wang, Baijing Wu, Youdong Wang, Cunpu Li, Minhua Shao, Bin Liu, Zidong Wei\",\"doi\":\"10.1021/acs.jpclett.4c02342\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"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<sub>2</sub>@PbO<sub>2</sub>@Ti electrode, which produces substituted lactones through a stepwise mechanism. PbO<sub>2</sub>, 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<sub>2</sub> 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.\",\"PeriodicalId\":62,\"journal\":{\"name\":\"The Journal of Physical Chemistry Letters\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":4.8000,\"publicationDate\":\"2024-10-10\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"The Journal of Physical Chemistry Letters\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.jpclett.4c02342\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry Letters","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1021/acs.jpclett.4c02342","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
A Stepwise Electrochemical Baeyer–Villiger Oxidation with Water as the Oxygen Source
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 CeO2@PbO2@Ti electrode, which produces substituted lactones through a stepwise mechanism. PbO2, in combination with a benzoic acid molecular catalyst, can generate and utilize reactive oxygen species from electrochemical water splitting to serve as the oxidant. CeO2 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.
期刊介绍:
The Journal of Physical Chemistry (JPC) Letters is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, chemical physicists, physicists, material scientists, and engineers. An important criterion for acceptance is that the paper reports a significant scientific advance and/or physical insight such that rapid publication is essential. Two issues of JPC Letters are published each month.