Mechanism of scandium ion catalyzed Diels-Alder reaction of anthracenes with methyl vinyl ketone

被引：13

作者：

Fukuzumi, S ^{[1
]}

Yuasa, J ^{[1
]}

Miyagawa, T ^{[1
]}

Suenobu, T ^{[1
]}

机构：

[1] Osaka Univ, Dept Mat & Life Sci, Grad Sch Engn, SORST,Japan Sci & Technol Corp, Suita, Osaka 5650871, Japan

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2005年 / 109卷 / 14期

关键词：

D O I：

10.1021/jp050347u

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 [物理化学]; 081704 [应用化学];

摘要：

Rates of Diels-Alder cycloadditions of anthracenes with methyl vinyl ketone (MVK) are accelerated significantly by the presence of scandium triflate [Sc(OTf)(3)], Sc(OTf)(3) also promotes photoinduced electron-transfer reactions from various electron donors to MVK significantly. Comparison of the promoting effect of Sc(OTf)(3) in photoinduced electron-transfer reactions of MVK with the catalytic effect of Sc(OTf)(3) in the Diels-Alder reaction of 9,10-dimethylanthracene with MVK has revealed that the MVK-Sc(OTf)(3) complex is a reactive intermediate in both the Diels-Alder and photoinduced electron-transfer reactions. The observed second-order rate constants of the Sc(OTf)(3)-Catalyzed Diels-Alder reactions of anthracenes with MVK are by far larger than those expected from the observed linear Gibbs energy relation for the Diels-Alder reactions of anthracenes with stronger electron acceptors than MVK, which are known to proceed via electron transfer. This indicates that the Sc(OTf)(3)-catalyzed Diels-Alder reactions of anthracenes with MVK does not proceed via an electron-transfer process from anthracences to the MVK-Sc(OTf)(3) complex.

引用

页码：3174 / 3181

页数：8

共 91 条

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