{"title":"Rhodium- and Iridium-Catalyzed (Enantioselective) Fluoroamidation of gem-Difluoroalkenes via Chelation Assistance","authors":"Heng Song, Ruijie Mi, Xingwei Li","doi":"10.1021/acscatal.5c00001","DOIUrl":null,"url":null,"abstract":"The incorporation of fluorine atoms into organics often significantly improved the lipophilicity and metabolic stability of pharmaceuticals. Herein, two classes of fluoroamidation reactions of <i>gem</i>-difluoroalkenes are described. Rhodium-catalyzed asymmetric 1,2-fluoroamidation of 4,4-difluoro-3-butenamide proceeded in excellent enantioselectivity to give a CF<sub>3</sub>-containing diamide using CsF as a convenient fluoride source. On the other hand, the 1,4-fluoroamidation of <i>gem</i>-difluoro-1,3-dienes required iridium catalysis using AgF as a fluoride source under mild reaction conditions. In both cases, fluorometalation occurs as a key elementary step, with a metal–alkyl intermediate being stabilized by chelation or allyl formation as a driving force.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"30 8 1","pages":""},"PeriodicalIF":13.1000,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Catalysis ","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acscatal.5c00001","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
The incorporation of fluorine atoms into organics often significantly improved the lipophilicity and metabolic stability of pharmaceuticals. Herein, two classes of fluoroamidation reactions of gem-difluoroalkenes are described. Rhodium-catalyzed asymmetric 1,2-fluoroamidation of 4,4-difluoro-3-butenamide proceeded in excellent enantioselectivity to give a CF3-containing diamide using CsF as a convenient fluoride source. On the other hand, the 1,4-fluoroamidation of gem-difluoro-1,3-dienes required iridium catalysis using AgF as a fluoride source under mild reaction conditions. In both cases, fluorometalation occurs as a key elementary step, with a metal–alkyl intermediate being stabilized by chelation or allyl formation as a driving force.
期刊介绍：
ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels.
The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.
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