Palladium-catalyzed hydrosilylation of ynones to access siliconstereogenic silylenones by stereospecific aromatic interactionassisted Si–H activation  

作　　者：Jia-Le Xie Zheng Xu Han-Qi Zhou Yi-Xue Nie Jian Cao Guan-Wu Yin Jean-Philippe Bouillon Li-Wen Xu 

机构地区：[1]Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education,Key Laboratory of Organosilicon Material Technology of Zhejiang Province,Hangzhou Normal University,Hangzhou 311121,China [2]State Key Laboratory for Oxo Synthesis and Selective Oxidation,Suzhou Research Institute(SRI),Lanzhou Institute of Chemical Physics(LICP),University of the Chinese Academy of Sciences(UCAS),Lanzhou 730000,China [3]Normandie University,INSA Rouen,UNIROUEN,CNRS,COBRA(UMR 6014),Rouen 76000,France

出　　处：《Science China Chemistry》2021年第5期761-769,共9页中国科学（化学英文版）

基　　金：This work was supported by the National Natural Science Foundation of China(21773051,22072035,21703051,21801056,21901056);Zhejiang Provincial Natural Science Foundation of China(LZ18B020001,LY18B020013,LQ19B040001).

摘　　要：Hydrosilylation is one of the most important reactions in synthetic chemistry and ranks as a fundamental method to access organosilicon compounds in industrial and academic processes.However,the enantioselective construction of chiral-at-silicon compounds via catalytic asymmetric hydrosilylation remained limited and difficult.Here we report a highly enantioselective hydrosilylation of ynones,a type of carbonyl-activated alkynes,using a palladium catalyst with a chiral binaphthyl phosphoramidite ligand.The stereospecific hydrosilylation of ynones affords a series of silicon-stereogenic silylenones with up to 94%yield,>20:1 regioselectivity and 98:2 enantioselectivity.The density functional theory(DFT)calculations were conducted to elucidate the reaction mechanism and origin of high degree of stereoselectivity,in which the powerful potential of aromatic interaction in this reaction is highlighted by the multiple C–H-πinteraction and aromatic cavity-oriented enantioselectivitydetermining step during desymmetric functionalization of Si–H bond.

关 键 词：asymmetric catalysis DFT calculations HYDROSILYLATION silicon-stereogenic vinylsilanes aromatic interaction 

分 类 号：O627.41[理学—有机化学]