Directed Metal (Oxo) Aliphatic C-H Hydroxylations: Overriding Substrate Bias

被引：184

作者：

Bigi, Marinus A. ^{[1
]}

Reed, Sean A. ^{[1
]}

White, M. Christina ^{[1
]}

机构：

[1] Univ Illinois, Dept Chem, Roger Adams Lab, Urbana, IL 61801 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2012年 / 134卷 / 23期

基金：

美国国家科学基金会;

关键词：

INTRAMOLECULAR HYDROGEN ABSTRACTION; TAXOL BIOSYNTHESIS; HYDROCARBON OXIDATION; CATALYTIC ADDITION; DIRECT ARYLATION; BOND ACTIVATION; MILD CONDITIONS; BENZOIC-ACIDS; OXYGENATION; COMPLEX;

D O I：

10.1021/ja301685r

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The first general strategy for a directing effect on metal (oxo)-promoted C-H hydroxylations is described. Carboxylic acid moieties on the substrate overcome unfavorable electronic, steric, and stereoelectronic biases in C-H hydroxylations catalyzed by the non-heme iron complex Fe(PDP). In a demonstration of the power of this directing effect, C-H oxidation is diverted away from an electronically favored C-1 H abstraction/rearrangement pathway in the paclitaxel framework to enable installation of C-2 oxidation in the naturally occurring oxidation state and stereoconfiguration.

引用

页码：9721 / 9726

页数：6

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