通过连续的拉罗克杂环化反应和硅基交叉偶联反应制备2,3-二取代吲哚。
Preparation of 2,3-Disubstituted Indoles by Sequential Larock Heteroannulation and Silicon-Based Cross-Coupling Reactions.
作者信息
Denmark Scott E, Baird John D
机构信息
Roger Adams Laboratory, Department of Chemistry, University of Illinois Urbana, IL 61801.
出版信息
Tetrahedron. 2009 Apr 18;65(16):3120-3129. doi: 10.1016/j.tet.2008.10.043.
Abstract
A simple and convergent synthesis of 2,3-disubstituted indoles has been developed using a sequential Larock indole synthesis and silicon-based, cross-coupling reaction. Substituted 2-iodoanilines reacted with an alkynyldimethylsilyl tert-butyl ether to afford indole-2-silanols under the Larock heteroannulation conditions after hydrolysis. The corresponding sodium 2-indolylsilanolate salts successfully engaged in cross-coupling with aryl bromides and chlorides to afford multi-substituted indoles. The development of an alkynyldimethylsilyl tert-butyl ether as a masked silanol equivalent enabled a smooth heteroannulation process and the identification of a suitable catalyst/ligand combination provided for a facile cross-coupling reaction.
摘要
通过连续的拉罗克吲哚合成和基于硅的交叉偶联反应，开发了一种简单且收敛的2,3-二取代吲哚的合成方法。取代的2-碘苯胺与炔基二甲基甲硅烷基叔丁基醚反应，在水解后于拉罗克杂环化条件下得到吲哚-2-硅醇。相应的2-吲哚基硅醇钠盐成功地与芳基溴化物和氯化物进行交叉偶联，得到多取代吲哚。将炔基二甲基甲硅烷基叔丁基醚作为掩蔽的硅醇等效物的开发实现了顺利的杂环化过程，并且鉴定出合适的催化剂/配体组合为简便的交叉偶联反应提供了条件。
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2
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