Enantioselective and stereodivergent hydromonofluoroalkylation of conjugated and remote diene  

作　　者：Qi-Ying Liao Chao Ma Yu-Chao Wang Shao-Qian Yang Jiang-Shan Ma Zhi-Tao He 

机构地区：[1]College of Chemistry and Materials Science,Sichuan Normal University,Chengdu 610068,China [2]CAS Key Laboratory of Synthetic Chemistry of Natural Substances,Shanghai Institute of Organic Chemistry,University of Chinese Academy of Sciences,Shanghai200032,China [3]School of Chemistry and Materials Science,Hangzhou Institute for Advanced Study,University of Chinese Academy of Sciences,Hangzhou 310024,China

出　　处：《Chinese Chemical Letters》2023年第12期159-165,共7页中国化学快报（英文版）

基　　金：the National Natural Science Foundation of China(NSFC,No.22071262);Science and Technology Commission of Shanghai Municipality(No.22ZR1475200);Shanghai Rising-Star program(No.20QA1411300);CAS Key Laboratory of Synthetic Chemistry of Natural Substances,and Shanghai Institute of Organic Chemistry for financial support.

摘　　要：Because of the widespread applications of optically active alkyl fluorides in medicinal and agro chem-icals,enantioselective and even stereodivergent construction of alkyl fluorides remains highly desirable but underdeveloped.Transition-metal-catalyzed asymmetric hydrofluoroalkylation of readily available di-enes represents a novel route to achieve this goal,yet receives scarce study.Here we report an intrigu-ing palladium-catalyzed enantioselective hydromonofluoroalkylation reaction of conjugated dienes.Both monosubstituted and internal dienes proceed well with the transformation and furnish alkyl fluorides in generally>80%yield and>90%ee.A stereodivergent hydromonofluoroalkylation protocol via Pd/Cu co-catalysis is also established for the access to all four stereoisomers of corresponding moieties bear-ing a fully-substituted F-stereogenic center and vicinal tertiary carbon center.In addition,asymmetric migratory hydromonofluoroalkylation of skipped dienes is developed to realize the direct allylic C-H flu-oroalkylation.A compound library of enantioenriched cyclic fluorides is thus built to highlight the trans-formation potential of present methodology.

关 键 词：Hydromonofluoroalkylation ENANTIOSELECTIVE Stereodivergent 1 3-Diene Remote diene 

分 类 号：O621.25[理学—有机化学]