{"title":"光诱导电荷转移复合物介导的脱羧磷酸化","authors":"Hailong He,Jiajin Chen,Hongyao Wang,Wenlong He,Tao Zhou,Zihao Chen,Zhiyan Xue,Qilong Wu,Ziyi Xu,Shuyang Liu,Yunhe Jin","doi":"10.1021/acs.orglett.6c04068","DOIUrl":null,"url":null,"abstract":"Phosphonium salts are valuable intermediates in organic synthesis, but their preparation often requires harsh conditions and specific carbon precursors. Herein, we report a photoinduced decarboxylative phosphoniumation of redox-active esters (RAEs) for the direct synthesis of alkyl and benzyl phosphonium salts. A photoresponsive ternary charge-transfer complex (CTC) formed from NaI, tertiary phosphines, and RAEs enables the reaction under transition-metal- and external-photocatalyst-free conditions. The method tolerates diverse benzyl and aliphatic RAEs and tertiary phosphines, including commercial phosphine ligand frameworks, and enables the late-stage phosphoniumation of complex carboxylic-acid-derived substrates.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"56 1","pages":""},"PeriodicalIF":4.7000,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Photoinduced Charge-Transfer Complex-Mediated Decarboxylative Phosphoniumation\",\"authors\":\"Hailong He,Jiajin Chen,Hongyao Wang,Wenlong He,Tao Zhou,Zihao Chen,Zhiyan Xue,Qilong Wu,Ziyi Xu,Shuyang Liu,Yunhe Jin\",\"doi\":\"10.1021/acs.orglett.6c04068\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Phosphonium salts are valuable intermediates in organic synthesis, but their preparation often requires harsh conditions and specific carbon precursors. Herein, we report a photoinduced decarboxylative phosphoniumation of redox-active esters (RAEs) for the direct synthesis of alkyl and benzyl phosphonium salts. A photoresponsive ternary charge-transfer complex (CTC) formed from NaI, tertiary phosphines, and RAEs enables the reaction under transition-metal- and external-photocatalyst-free conditions. The method tolerates diverse benzyl and aliphatic RAEs and tertiary phosphines, including commercial phosphine ligand frameworks, and enables the late-stage phosphoniumation of complex carboxylic-acid-derived substrates.\",\"PeriodicalId\":54,\"journal\":{\"name\":\"Organic Letters\",\"volume\":\"56 1\",\"pages\":\"\"},\"PeriodicalIF\":4.7000,\"publicationDate\":\"2026-10-20\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organic Letters\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.orglett.6c04068\",\"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 Letters","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.orglett.6c04068","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
Phosphonium salts are valuable intermediates in organic synthesis, but their preparation often requires harsh conditions and specific carbon precursors. Herein, we report a photoinduced decarboxylative phosphoniumation of redox-active esters (RAEs) for the direct synthesis of alkyl and benzyl phosphonium salts. A photoresponsive ternary charge-transfer complex (CTC) formed from NaI, tertiary phosphines, and RAEs enables the reaction under transition-metal- and external-photocatalyst-free conditions. The method tolerates diverse benzyl and aliphatic RAEs and tertiary phosphines, including commercial phosphine ligand frameworks, and enables the late-stage phosphoniumation of complex carboxylic-acid-derived substrates.
期刊介绍:
Organic Letters invites original reports of fundamental research in all branches of the theory and practice of organic, physical organic, organometallic,medicinal, and bioorganic chemistry. Organic Letters provides rapid disclosure of the key elements of significant studies that are of interest to a large portion of the organic community. In selecting manuscripts for publication, the Editors place emphasis on the originality, quality and wide interest of the work. Authors should provide enough background information to place the new disclosure in context and to justify the rapid publication format. Back-to-back Letters will be considered. Full details should be reserved for an Article, which should appear in due course.