C-H Acidity and Arene Nucleophilicity as Orthogonal Control of Chemoselectivity in Dual C-H Bond Activation

被引：23

作者：

Liu, Ji-Ren ^{[1
]}

Duan, Ye-Qing ^{[2
]}

Zhang, Shuo-Qing ^{[1
]}

Zhu, Lu-Jing ^{[1
]}

Jiang, Yuan-Ye ^{[2
]}

Bi, Siwei ^{[2
]}

Hong, Xin ^{[1
]}

机构：

[1] Zhejiang Univ, Dept Chem, Hangzhou 310027, Zhejiang, Peoples R China

[2] Qufu Normal Univ, Sch Chem & Chem Engn, Qufu 273165, Peoples R China

来源：

ORGANIC LETTERS | 2019年 / 21卷 / 07期

基金：

中国博士后科学基金;

关键词：

ARYLATION; GOLD; DISTORTION/INTERACTION; FUNCTIONALIZATION;

D O I：

10.1021/acs.orglett.9b00633

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

We discovered a cooperative gold/silver catalysis mechanism in the oxidative cross-coupling reaction between 1,2,4,5-tetrafluorobenzene and N-TIPS-indole, using DFT calculations. A silver(I)-catalyzed CMD mechanism is responsible for the C-H activation of 1,2,4,5-tetrafluorobenzene, and C-H acidity determines the chemoselectivity. A gold(III)-catalyzed S(E)2Ar mechanism is responsible for the C3-H activation of N-TIPS-indole, and arene nucleophilicity determines the chemo- and regioselectivity. The orthogonal chemoselectivity control provides a mechanistic guide for dual C-H activation reactions.

引用

页码：2360 / 2364

页数：5

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