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.
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)。
