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微波辅助闭环复分解反应再探讨。关于非热微波效应问题。

Microwave-assisted ring-closing metathesis revisited. On the question of the nonthermal microwave effect.

作者信息

Garbacia Stefania, Desai Bimbisar, Lavastre Olivier, Kappe C Oliver

机构信息

Institut de Chimie, UMR 6509 Universite de Rennes 1-CNRS, Campus de Beaulieu, 35042 Rennes, France.

出版信息

J Org Chem. 2003 Nov 14;68(23):9136-9. doi: 10.1021/jo035135c.

Abstract

The ring-closing metathesis reactions (RCM) of six standard diene substrates leading to five-, six-, or seven-membered carbo- or heterocycles were investigated under controlled microwave irradiation. RCM protocols were performed with standard Grubbs type II and a cationic ruthenium allenylidene catalyst in neat and ionic liquid-doped methylene chloride under sealed vessel conditions. Very rapid conversions (15 s) were achieved utilizing 0.5 mol % Grubbs II catalyst under microwave conditions. Careful comparison studies indicate that the observed rate enhancements are not the result of a nonthermal microwave effect.

摘要

在可控微波辐射下,研究了六种标准二烯底物发生关环复分解反应(RCM)生成五元、六元或七元碳环或杂环的情况。在密封容器条件下,使用标准的格拉布(Grubbs)二代催化剂和阳离子钌亚烷基丙二烯催化剂,分别在纯溶剂以及离子液体掺杂的二氯甲烷中进行RCM反应。在微波条件下,使用0.5 mol%的格拉布二代催化剂可实现非常快速的转化(15秒)。仔细的对比研究表明,观察到的速率提高并非非热微波效应的结果。

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