Exploring Diradical Chemistry: A Carbon-Centered Radical May Act as either an Anion or Electrophile through an Orbital Isomer

被引：13

作者：

Goncalves, Theo P. ^{[1
]}

Mohamed, Mubina ^{[1
]}

Whitby, Richard J. ^{[1
]}

Sneddon, Helen F. ^{[2
]}

Harrowven, David C. ^{[1
]}

机构：

[1] Univ Southampton, Chem, Southampton SO17 1BJ, Hants, England

[2] GlaxoSmithKline, Stevenage SG1 2NY, Herts, England

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2015年 / 54卷 / 15期

基金：

英国工程与自然科学研究理事会;

关键词：

density functional calculations; flow chemistry; radicals; rearrangements; small ring systems; MYERS-SAITO; CYCLOBUTENONE REARRANGEMENTS; RING EXPANSION; CYCLIZATION; 4-ALKYNYLCYCLOBUTENONES; BENZYNE; PARENT; CYCLOAROMATIZATION; GENERATION; REACTIVITY;

D O I：

10.1002/anie.201411334

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Diradical intermediates, formed by thermolysis of alkynylcyclobutenones, can display radical, anion, or electrophilic character because of the existence of an orbital isomer with zwitterionic and cyclohexatrienone character. Our realization that water, alcohols, and certain substituents can induce the switch provides new opportunities in synthesis. For example, it can be used to shut down radical pathways and to give access to aryl carbonates and tetrasubstituted quinones.

引用

页码：4531 / 4534

页数：4