Citation: Yujia Shi, Yan Qiao, Pengfei Xie, Miaomiao Tian, Xingwei Li, Junbiao Chang, Bingxian Liu. Rhodium-catalyzed enantioselective in situ C(sp³)−H heteroarylation by a desymmetrization approach[J]. Chinese Chemical Letters, ;2024, 35(10): 109544. doi: 10.1016/j.cclet.2024.109544 shu

Rhodium-catalyzed enantioselective in situ C(sp³)−H heteroarylation by a desymmetrization approach

Yujia Shi ^a ,
Yan Qiao ^b ,
Pengfei Xie ^a ,
Miaomiao Tian ^a ,
Xingwei Li ^a ,
Junbiao Chang ^a ,
Bingxian Liu ^{a, *,}

a.
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
b.
Department of Pathophysiology, School of Basic Medical Sciences, Zhengzhou University, Zhengzhou 450001, China

liubx1120@htu.edu.cn

Received Date: 9 October 2023
Revised Date: 8 January 2024
Accepted Date: 15 January 2024
Available Online: 21 January 2024

Figures(5)

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.
- Heteroarylation,
- C(sp³)−H activation,
- Enantioselective,
- Desymmetrization,
- π Interactions
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沈阳化工大学材料科学与工程学院沈阳 110142

Rhodium-catalyzed enantioselective in situ C(sp3)−H heteroarylation by a desymmetrization approach

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通讯作者: 陈斌, bchen63@163.com

Rhodium-catalyzed enantioselective in situ C(sp³)−H heteroarylation by a desymmetrization approach