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 

作者机构：State Key Laboratory for Oxo Synthesis and Selective OxidationCenter for Excellence in Molecular SynthesisSuzhou Research Institute of LICPLanzhou Institute of Chemical Physics(LICP)Chinese Academy of SciencesLanzhou 730000 State Key Laboratory of Element-Organic ChemistryCollege of ChemistryNankai UniversityTianjin 300071 University of Chinese Academy of SciencesBeijing 100049 

出 版 物：《CCS Chemistry》 (中国化学会会刊（英文）)

年 卷 期：2021年第3卷第6期

页      面：1678-1689页

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 

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 

主　　题：fluorine effect monofluoroalkene Julia-Kocienski fluoroolefination DFT calculation frontier molecular orbital 

摘      要：Classical Julia-Kocienski fluoroolefination represents an indispensable platform for the construction of ***,its complex multistep mechanistic manifold along with the unrevealed intrinsic“fluorine effectin nucleophilic reactions might be responsible for the difficult control of the original stereoselectivity and is thus often ambiguous to ***,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 *** functional theory(DFT)investigations indicate the fluorine substituents can activate the C-C and C-S bond leading toα-elimination by antiphase orbital *** rate-limiting step were calculated via fourmembered transition states with ring *** the sterically eclipsed repulsion and secondary orbital interaction affect the stereoselectivity.