Fine-Tuning the Oxidative Ability of Persistent Radicals: Electrochemical and Computational Studies of Substituted 2-Pyridylhydroxylamines

被引：28

作者：

Bogart, Justin A. ^{[1
]}

Lee, Heui Beom ^{[1
]}

Boreen, Michael A. ^{[1
]}

Jun, Minsik ^{[1
]}

Schelter, Eric J. ^{[1
]}

机构：

[1] Univ Penn, Dept Chem, P Roy & Diana T Vagelos Labs, Philadelphia, PA 19104 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2013年 / 78卷 / 12期

基金：

美国国家科学基金会;

关键词：

ELECTRON-TRANSFER KINETICS; NITROXIDE RADICALS; REDUCTION POTENTIALS; NICKEL(II) COMPLEXES; REAGENTS BEARING; REDOX MEDIATORS; CHELATE LIGAND; EXCHANGE; CHEMISTRY; ARYLMAGNESIUM;

D O I：

10.1021/jo400944r

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

N-tert-Butyl-N-2-pyridylhydroxylamines were synthesized from 2-halopyridines and 2-methyl-2-nitrosopropane using magnesium halogen exchange. The use of Turbo Grignard generated the metallo-2-pyridyl intermediate more reliably than alkyllithium reagents. The hydroxylamines were characterized using NMR, electrochemistry, and density functional theory. Substitution of the pyridyl ring in the 3-, 4-, and 5-positions was used to vary the potential of the nitroxyl/oxoammonium redox couple by 0.95 V. DFT computations of the electrochemical properties agree with experiment and provide a toolset for the predictive design of pyridyl nitroxides.

引用

页码：6344 / 6349

页数：6

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