{"title":"Photoexcited Palladium-Catalyzed Defluorinative 1,2-Functional-Group Migration of Allylic Alcohols","authors":"Xinyue Ma, Qianqian Li, Wei Sun, Zhijun Zuo","doi":"10.1021/acs.orglett.6c03929","DOIUrl":null,"url":null,"abstract":"<p>Interception\r\nof aryldifluoromethyl radicals by unactivated alkenes\r\nis typically limited to 1,2-difunctionalization. We report a photoexcited\r\npalladium-catalyzed defluoroalkylative rearrangement that combines\r\nselective monodefluorination of trifluoromethylarenes, radical addition,\r\nlocal 1,2-migration, and carbonyl formation. The redox-neutral cascade\r\nachieves formal 1,2,3-trifunctionalization of allylic alcohols, providing\r\nα-alkynyl, α-aryl, and α-heteroaryl β-(aryldifluoromethyl)\r\nketones with broad functional-group compatibility and without stoichiometric\r\noxidants, thereby redirecting postaddition alkyl radicals from conventional\r\ntermination toward migration-enabled skeletal reorganization under\r\nvisible-light irradiation in a single operation.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"28 41","pages":"13064–13069"},"PeriodicalIF":4.7000,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic Letters","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.orglett.6c03929","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2026/10/5 0:00:00","PubModel":"Epub","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
引用次数: 0
Abstract
Interception
of aryldifluoromethyl radicals by unactivated alkenes
is typically limited to 1,2-difunctionalization. We report a photoexcited
palladium-catalyzed defluoroalkylative rearrangement that combines
selective monodefluorination of trifluoromethylarenes, radical addition,
local 1,2-migration, and carbonyl formation. The redox-neutral cascade
achieves formal 1,2,3-trifunctionalization of allylic alcohols, providing
α-alkynyl, α-aryl, and α-heteroaryl β-(aryldifluoromethyl)
ketones with broad functional-group compatibility and without stoichiometric
oxidants, thereby redirecting postaddition alkyl radicals from conventional
termination toward migration-enabled skeletal reorganization under
visible-light irradiation in a single operation.
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.
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