A Straightforward Route to Potent Phenolic Chain-Breaking Antioxidants by Acid-Promoted Transposition of 1,4-Benzo[b]oxathiines to Dihydrobenzo[b]thiophenes

被引：15

作者：

Viglianisi, Caterina ^{[1
]}

Amorati, Riccardo ^{[2
]}

Di Pietro, Leonardo ^{[1
]}

Menichetti, Stefano ^{[1
]}

机构：

[1] Univ Florence, Dept Chem Ugo Schiff, I-50019 Florence, Italy

[2] Univ Bologna, Dept Chem G Ciamician, I-40126 Bologna, Italy

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2015年 / 21卷 / 46期

关键词：

antioxidants; electrophilic substitution; phenols; S heterocycles; vitamins; HYDROXY-SUBSTITUTED; 4-THIAFLAVANES; POLYHYDROXYLATED; 4-THIAFLAVANS; ELECTROPHILIC ADDITIONS; ASYMMETRIC-SYNTHESIS; O-THIOQUINONES; VITAMIN-E; REACTIVITY; SULFUR; THIIRANIUM; IONS;

D O I：

10.1002/chem.201502650

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The transformation of simple phenols with limited antioxidant activity into potent chain-breaking antioxidants was achieved by a three-step protocol, consisting of the conversion of phenols into 1,4-benzo[b]oxathiines followed by an unprecedented acid-promoted transposition to o-hydroxydihydrobenzo[b]thiophenes, or dihydrobenzo[de]thiochromenes, starting from phenols or naphthols, respectively. These derivatives, bearing a benzo-fused heterocycle with a sulfide sulfur ortho to the phenolic OH, have a rate constant of reaction with alkylperoxyl radicals (k(inh)) comparable to that of -tocopherol. A solid rationale for the transposition mechanism as well as for the structure-antioxidant activity relationship is presented.

引用

页码：16639 / 16645

页数：7

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