{"title":"使用硫酰氟对羧酸进行脱羧官能化的高效平台:钯催化烷基羧酸的脱羧脱氢反应和非烷基羧酸的脱羧交叉偶联反应","authors":"Chenfei Guan, huijie Qi, Linjun Han, Guofu Zhang, Jinghui Lyu, Chengrong Ding","doi":"10.1039/d4qo00428k","DOIUrl":null,"url":null,"abstract":"Decarboxylation functionalization of carboxylic acids has evolved to valuable synthetic methods because of the structural diversity of carboxylic acids and their utility in drug discovery as directing groups for C–H activation. Although transition-metal-catalyzed decarboxylation is one of the most common methods, it typically requires complex operations and additives within a limited substrate scope. In this study, we show that the use of a palladium-catalyzed system together with sulfuryl fluoride can readily effect decarboxylative dehydrogenation and decarboxylative cross-coupling of various alkyl and aryl carboxylic acids. Based on mechanistic studies including DFT calculations, a detailed catalytic cycle is presented in which rapid generation of an acyl fluoride from the reaction of SO2F2 with a carboxylic acid is critical for initiating catalysis. The versatility of a new mediator platform has been demonstrated with a diverse range of substrates and applications.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":4.6000,"publicationDate":"2024-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"An efficient platform for decarboxylative functionalization of carboxylic acids using sulfuryl fluoride: Pd-catalyzed decarboxylative dehydrogenation of alkanecarboxylic acids and decarboxylative cross-coupling of arenecarboxylic acids\",\"authors\":\"Chenfei Guan, huijie Qi, Linjun Han, Guofu Zhang, Jinghui Lyu, Chengrong Ding\",\"doi\":\"10.1039/d4qo00428k\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Decarboxylation functionalization of carboxylic acids has evolved to valuable synthetic methods because of the structural diversity of carboxylic acids and their utility in drug discovery as directing groups for C–H activation. Although transition-metal-catalyzed decarboxylation is one of the most common methods, it typically requires complex operations and additives within a limited substrate scope. In this study, we show that the use of a palladium-catalyzed system together with sulfuryl fluoride can readily effect decarboxylative dehydrogenation and decarboxylative cross-coupling of various alkyl and aryl carboxylic acids. Based on mechanistic studies including DFT calculations, a detailed catalytic cycle is presented in which rapid generation of an acyl fluoride from the reaction of SO2F2 with a carboxylic acid is critical for initiating catalysis. The versatility of a new mediator platform has been demonstrated with a diverse range of substrates and applications.\",\"PeriodicalId\":97,\"journal\":{\"name\":\"Organic Chemistry Frontiers\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":4.6000,\"publicationDate\":\"2024-06-06\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organic Chemistry Frontiers\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1039/d4qo00428k\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, ORGANIC\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic Chemistry Frontiers","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4qo00428k","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
An efficient platform for decarboxylative functionalization of carboxylic acids using sulfuryl fluoride: Pd-catalyzed decarboxylative dehydrogenation of alkanecarboxylic acids and decarboxylative cross-coupling of arenecarboxylic acids
Decarboxylation functionalization of carboxylic acids has evolved to valuable synthetic methods because of the structural diversity of carboxylic acids and their utility in drug discovery as directing groups for C–H activation. Although transition-metal-catalyzed decarboxylation is one of the most common methods, it typically requires complex operations and additives within a limited substrate scope. In this study, we show that the use of a palladium-catalyzed system together with sulfuryl fluoride can readily effect decarboxylative dehydrogenation and decarboxylative cross-coupling of various alkyl and aryl carboxylic acids. Based on mechanistic studies including DFT calculations, a detailed catalytic cycle is presented in which rapid generation of an acyl fluoride from the reaction of SO2F2 with a carboxylic acid is critical for initiating catalysis. The versatility of a new mediator platform has been demonstrated with a diverse range of substrates and applications.
期刊介绍:
Organic Chemistry Frontiers is an esteemed journal that publishes high-quality research across the field of organic chemistry. It places a significant emphasis on studies that contribute substantially to the field by introducing new or significantly improved protocols and methodologies. The journal covers a wide array of topics which include, but are not limited to, organic synthesis, the development of synthetic methodologies, catalysis, natural products, functional organic materials, supramolecular and macromolecular chemistry, as well as physical and computational organic chemistry.