Investigating the Reactivity of Radical Cations: Experimental and Computational Insights into the Reactions of Radical Cations with Alcohol and p-Toluene Sulfonamide Nucleophiles

被引：59

作者：

Campbell, John M. ^{[1
]}

Xu, Hai-Chao ^{[1
]}

Moeller, Kevin D. ^{[1
]}

机构：

[1] Washington Univ, St Louis, MO 63130 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2012年 / 134卷 / 44期

基金：

美国国家科学基金会;

关键词：

OLEFIN COUPLING REACTIONS; RING-OPENING REACTION; DENSITY FUNCTIONALS; AB-INITIO; HETEROLYSIS REACTIONS; CYCLIZATION; ELECTROCHEMISTRY; COMPETITION; MOLECULES; KINETICS;

D O I：

10.1021/ja307046j

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The reactivity of electrochemically generated radical cations toward alcohol and p-toluene sulfonamide nucleophiles was directly investigated through competition experiments. Alcohol-trapping of the radical cation is the kinetically favored pathway and is reversible. Trapping with the sulfonamide leads to the thermodynamic product. Both reaction pathways were investigated computationally with density functional theory (UB3LYP/6-31G(d)) calculations.

引用

页码：18338 / 18344

页数：7

共 52 条

[1]

[Anonymous], 2010, ANGEW CHEM INT ED, V49, P6106

[2] Direct detection of ion pair formation and collapse in a migration reaction of a β-phosphate radical [J].