Substituent-dictated partitioning of intermediates on the sulfide singlet oxygen reaction surface.: A new mechanism for oxidative C-S bond cleavage in α-hydroperoxy sulfides

被引：39

作者：

Toutchkine, A ^{[1
]}

Aebisher, D ^{[1
]}

Clennan, EL ^{[1
]}

机构：

[1] Univ Wyoming, Dept Chem, Laramie, WY 82071 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2001年 / 123卷 / 21期

关键词：

D O I：

10.1021/ja004188y

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The reactions of singlet oxygen with 17 sulfides bearing either anion or radical stabilizing substituents are reported. The abilities of substituents to modify product compositions in both the oxidative cleavage and sulfide oxidation pathways are analyzed in terms of partitioning of the hydroperoxy sulfonium ylide intermediate. Evidence is presented that suggests that the hydroperoxy sulfonium ylide exists in both diradical and zwitterionic forms. In addition, both inter- and intramolecular pathways for decomposition of a-hydroperoxy sulfides are suggested to rationalize the substituent-dependent formation of oxidative C-S bond cleavage products.

引用

页码：4966 / 4973

页数：8

共 30 条

[1] NOVEL ADDUCTS OF SULFIDES AND 4-SUBSTITUTED 1,2,4-TRIAZOLINE-3,5-DIONES (TAD) - A SIMILARITY OF TAD AND SINGLET OXYGEN O-1(2) [J].