Ruthenium(salen)-catalyzed aerobic oxidative desymmetrization of meso-diols and its kinetics

被引：100

作者：

Shimizu, H ^{[1
]}

Onitsuka, S ^{[1
]}

Egami, H ^{[1
]}

Katsuki, T ^{[1
]}

机构：

[1] Kyushu Univ, Dept Chem, Fac Sci, Grad Sch,CREST,Japan Sci & Technol Agcy,JST, Fukuoka 8128581, Japan

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2005年 / 127卷 / 15期

关键词：

D O I：

10.1021/ja047608i

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Chiral (nitrosyl)ruthenium(salen) complexes were found to be efficient catalysts for aerobic oxidative desymmetrization of meso-diols under photoirradiation to give optically active lactols. The scope of the applicability of this reaction ranges widely from acyclic diols to mono-cyclic diols, although fine ligand-tuning of the ruthenium(salen) complexes was required to attain high enantioselectivity (up to 93% ee). In particular, the nature of the apical ligand was found to affect not only enantioselectivity but also kinetics of the desymmetrization reaction. Spectroscopic analysis of the oxidation disclosed that irradiation of visible light is indispensable not only for dissociation of the nitrosyl ligand but also for single electron transfer from the alcohol-bound ruthenium ion to dioxygen.

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页码：5396 / 5413

页数：18

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