Ag(I)-C-H Activation Enables Near-Room-Temperature Direct α-Arylation of Benzo[b]thiophenes

被引：90

作者：

Colletto, Chiara ^{[1
]}

Panigrahi, Adyasha ^{[1
]}

Fernandez-Casado, Jaime ^{[1
]}

Larrosa, Igor ^{[1
]}

机构：

[1] Univ Manchester, Sch Chem, Oxford Rd, Manchester M13 9PL, Lancs, England

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2018年 / 140卷 / 30期

基金：

英国工程与自然科学研究理事会; 欧洲研究理事会;

关键词：

CATALYZED DIRECT ARYLATION; H BOND ARYLATION; PROGRESS KINETIC-ANALYSIS; ARYL CHLORIDES; HETEROAROMATIC-COMPOUNDS; HETEROARENES; HETEROCYCLES; THIOPHENES; EFFICIENT; BROMIDES;

D O I：

10.1021/jacs.8b05361

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The first example of near-room-temperature alpha-arylation of benzo[b]thiophenes is reported. The discovery rests on the observation of a switch in alpha-/beta-regioselectivity at different loadings of Pcl(2)(dba)(3)center dot CHCl3 in the coupling between benzo[b]thiophene and 4-iodotoluene. We show that this unprecedented regioselectivity switch is driven by a Ag(I)-mediated C-H activation at the alpha-C-H position, which becomes the dominant mode of reactivity at low concentrations of Pd. Competition experiments, kinetic studies, KIE, and D/H scrambling experiments have been carried out supporting this mechanism.

引用

页码：9638 / 9643

页数：6

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