Oxidatively Induced C-H Activation at High Valent Nickel

被引：55

作者：

Chong, Eugene ^{[1
]}

Kampf, Jeff W. ^{[1
]}

Ariafard, Alireza ^{[2
]}

Canty, Allan J. ^{[2
]}

Sanford, Melanie S. ^{[1
]}

机构：

[1] Univ Michigan, Dept Chem, 930 N Univ Ave, Ann Arbor, MI 48109 USA

[2] Univ Tasmania, Sch Phys Sci, Hobart, Tas 7001, Australia

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2017年 / 139卷 / 17期

基金：

加拿大自然科学与工程研究理事会;

关键词：

REDUCTIVE ELIMINATION; ELECTROPHILIC FLUORINATION; COUPLING REACTIONS; BOND ACTIVATION; COMPLEXES; NI(II); NI; PLATINUM(IV); PALLADIUM; REACTIVITY;

D O I：

10.1021/jacs.7b02387

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

This communication describes a series of oxidatively induced intramolecular arene C-H activation reactions of Ni-II model complexes to yield Ni-IV sigma-aryl products. These reactions proceed within to min at room temperature, which represents among the mildest conditions reported for C-H cleavage at a Ni center. A combination of density functional theory and preliminary experimental mechanistic studies implicate a pathway involving initial 2e(-) oxidation of the Ni-II starting materials by the transfer reagent N-fluoro-2,4,6-trimethylpyr-idinium triflate followed by triflate-assisted C-H cleavage at Ni-IV to yield the products.

引用

页码：6058 / 6061

页数：4

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