Rhodium-catalyzed enantioselective in situ C(sp3)−H heteroarylation by a desymmetrization approach
Chinese Chemical Letters(2024)
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···π interactions 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.
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关键词
Heteroarylation,C(sp3)−H activation,Enantioselective,Desymmetrization,π Interactions
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