Distortion/Interaction Analysis Reveals the Origins of Selectivities in Iridium-Catalyzed C-H Borylation of Substituted Arenes and 5-Membered Heterocycles

被引：240

作者：

Green, Aaron G. ^{[1
]}

Liu, Peng ^{[1
]}

Merlic, Craig A. ^{[1
]}

Houk, K. N. ^{[1
]}

机构：

[1] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2014年 / 136卷 / 12期

基金：

美国国家科学基金会;

关键词：

1,3-DIPOLAR CYCLOADDITIONS; OLEFIN METATHESIS; BOND ACTIVATION; COMPLEXES; FUNCTIONALIZATION; REGIOSELECTIVITY; HETEROARENES; MECHANISM; LIGAND; BIS(PINACOLATO)DIBORON;

D O I：

10.1021/ja411699u

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The iridium-catalyzed borylation of mono- and disubstituted arenes and heteroarenes has been studied with density functional theory. The distortion/interaction model was employed to understand the origins of selectivities in these reactions. Computations revealed that the transition states for C-H oxidative addition are very late, resembling the aryl iridium hydride intermediate with a fully formed Ir-C bond. Consequently, the regioselectivity is mainly controlled by differences in the interaction energies between the iridium catalyst and arene carbon.

引用

页码：4575 / 4583

页数：9

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