Rhodium-catalyzed enantioselective in situ C(sp^(3))-H heteroarylation by a desymmetrization approach  

作　　者：Yujia Shi Yan Qiao Pengfei Xie Miaomiao Tian Xingwei Li Junbiao Chang Bingxian Liu 

机构地区：[1]State Key Laboratory of Antiviral Drugs,NMPA Key Laboratory for Research and Evaluation of Innovative Drug,School of Chemistry and Chemical Engineering,Henan Normal University,Pingyuan Laboratory,Xinxiang 453007,China [2]Department of Pathophysiology,School of Basic Medical Sciences,Zhengzhou University,Zhengzhou 450001,China

出　　处：《Chinese Chemical Letters》2024年第10期218-222,共5页中国化学快报（英文版）

基　　金：financial support for this work from the National Key R&D Program of China(No.2021YFC0864700);the National Natural Science Foundation of China(Nos.21801066,U1804283 and 82130103);the Central Plains Scholars and Scientists Studio Fund(No.2018002);the project funded by the Natural Science Foundation of Henan(Nos.222300420056,222300420204);the China Postdoctoral Science Foundation(Nos.2020M682307,2021T140183)。

摘　　要：A rhodium-catalyzed desymmetrization reaction for enantioselective methyl C-H arylation is achieved by utilizing an in situ arylating reagent via nucleophilic cyclization of o-aminoaryl alkyne.The reaction results in chiral indoles containing all-carbon quaternary stereocenters under atmospheric conditions,with a wide range of substrates exhibiting good enantioselectivity(44 examples).Mechnism and DFT studies show that the stereocontrol is reasonably achieved through the collaborative control of a large silicon substituted chiral ligand and C-H···π,LP···πinteractions between aryl rings of the carboxylate group and the substrate.Control experiments demonstrate that Rh-aryl bond formation via in situ nucleophilic cyclization is more critical for reaction efficiency than via C-H activation of the nucleophilic cyclization byproduct.

关 键 词：Heteroarylation C(sp^(3))-H activation ENANTIOSELECTIVE DESYMMETRIZATION πInteractions 

分 类 号：O621.251[理学—有机化学]