Fine-Tuning the Oxidative Ability of Persistent Radicals: Electrochemical and Computational Studies of Substituted 2-Pyridylhydroxylamines
Fine-Tuning the Oxidative Ability of Persistent Radicals: Electrochemical and Computational Studies of Substituted 2-Pyridylhydroxylamines
复制标题
DOI：
10.1021/jo400944r
复制
发表时间：
2013-06-21
影响因子：
3.6
通讯作者：
Schelter, Eric J.
中科院分区：
文献类型：
--
作者：
Bogart, Justin A.;Lee, Heui Beom;Schelter, Eric J.
以2-卤代吡啶和2-甲基-2-亚硝基丙烷为原料，用卤素镁交换法合成了N-叔丁基-N-2-吡啶羟胺。使用Turbo Grignard比烷基锂试剂更可靠地产生金属-2-吡啶中间体。用核磁共振、电化学和密度泛函理论对羟胺进行了表征。通过取代3-、4-和5-位上的吡啶环，使氮氧基/氧铵氧化还原电偶的电势变化了0.95V。密度泛函理论计算的电化学性质与实验相符，为吡啶氮氧化物的预测性设计提供了工具。
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.