Fluorine Effects for Tunable C-C and C-S Bond Cleavage in Fluoro-Julia-Kocienski Intermediates  

作　　者：Lei Kang Yongjia Lin Zeng Gao Jinlong Zhang Huameng Yang Jinlong Qian Qian Peng Gaoxi Jiang 

机构地区：[1]State Key Laboratory for Oxo Synthesis and Selective Oxidation,Center for Excellence in Molecular Synthesis,Suzhou Research Institute of LICP,Lanzhou Institute of Chemical Physics(LICP),Chinese Academy of Sciences,Lanzhou 730000 [2]State Key Laboratory of Element-Organic Chemistry,College of Chemistry,Nankai University,Tianjin 300071 [3]University of Chinese Academy of Sciences,Beijing 100049

出　　处：《CCS Chemistry》2021年第6期1678-1689,共12页中国化学会会刊（英文）

基　　金：The authors gratefully acknowledge the National Natural Science Foundation of China(nos.21602231,21890722,21702109,and 11811530637);Chinese Academy of Sciences“Light of West China”Program,and the Natural Science Foundation of Jiangsu Province(nos.BK20160396 and BK20191197);the Natural Science Foundation of Tianjin Municipality(nos.18JCYBJC21400 and 19JCJQJC62300);Tianjin Research Innovation Project for Postgraduate Students(no.2019YJSB081);the Fundamental Research Funds for Central Universities[Nankai University(nos.63191515 and 63196021)]for generous financial support.

摘　　要：Classical Julia-Kocienski fluoroolefination represents an indispensable platform for the construction of monofluoroalkenes.Nevertheless,its complex multistep mechanistic manifold along with the unrevealed intrinsic“fluorine effect”in nucleophilic reactions might be responsible for the difficult control of the original stereoselectivity and is thus often ambiguous to predict.Herein,a novel strategy involving the defined fluorine effect and new reaction mechanism was developed for tunable C-C and C-S bond cleavage,providing a versatile avenue for highly stereoselective and easily scalable construction of diverse monofluoroalkenes.Density functional theory(DFT)investigations indicate the fluorine substituents can activate the C-C and C-S bond leading toα-elimination by antiphase orbital interaction.The rate-limiting step were calculated via fourmembered transition states with ring strain.Both the sterically eclipsed repulsion and secondary orbital interaction affect the stereoselectivity.

关 键 词：fluorine effect monofluoroalkene Julia-Kocienski fluoroolefination DFT calculation frontier molecular orbital 

分 类 号：O62[理学—有机化学]