Diastereoselective Construction of α-Fluoroalkyl Cycloalkanols via Radical Alkylation of α-Fluoroalkyl Ketones  

作　　者：Yi Liu Ji Li Yulu Zhou Hanliang Zheng Zhenlu Shen Gangguo Zhu 

机构地区：[1]Key Laboratory of the Ministry of Education for Advanced Catalysis Materials,Department of Chemistry,Zhejiang Normal University,688 Yingbin Road,Jinhua,Zhejiang,321004 China [2]College of Chemical Engineering,Zhejiang University of Technology,Hangzhou,Zhejiang,310032 China

出　　处：《Chinese Journal of Chemistry》2023年第23期3275-3280,共6页中国化学（英文版）

基　　金：supported by the National Natural Science Foundation of China(22071218 and 22203076);the Natural Science Foundation of Zhejiang Province(LZ20B020001 and LY23B020004);the Ten Thousand Talents Plan of Zhejiang Province(2020R52021);the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang Province(2022R01007);Key Laboratory of Green Pesticides and Cleaner Production Technology of Zhejiang Province.

摘　　要：α-Fluoroalkyl (Rf) alcohols are privileged motifs in drugs and pharmaceutically active compounds.As such,it is highly desirable to develop efficient methods for assembling these scaffolds.Herein,a visible-light-induced cascade radical cyclization of alkenyl fluoroalkyl ketones is developed,producing a variety of decorate α-Rf cycloalkanols in promising yields with up to >20 : 1 dr selectivity.A radical chain mechanism involving an intramolecular radical addition to the α-Rf carbonyl group and a subsequent intermolecular hydrogen atom transfer (HAT) has been proposed.Density functional theory (DFT) calculations indicate that a fluorine effect contributes to the radical addition to carbonyls by lowering the π* (C=O) orbital energy of CORf and energy barrier of the HAT between alkoxy radicals and THF,which may be valuable for controllable transformations of fluorinated molecules.

关 键 词：Radical reactions CYCLIZATION ALKYLATION α-Fluoroalkyl ketones Fluorine effect ALCOHOLS 

分 类 号：O62[理学—有机化学]