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烯丙醇与烯烃的脱水交叉偶联反应。

Dehydrative cross-coupling reactions of allylic alcohols with olefins.

作者信息

Gumrukcu Yasemin, de Bruin Bas, Reek Joost N H

机构信息

Van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam (The Netherlands), Fax: (+31) 20 525 5604.

出版信息

Chemistry. 2014 Aug 25;20(35):10905-9. doi: 10.1002/chem.201404026. Epub 2014 Aug 11.

Abstract

The direct dehydrative activation of allylic alcohols and subsequent cross-coupling with alkenes by using palladium catalyst containing a phosphoramidite ligand is described. The activation of the allyl alcohol does not require stoichiometric additives, thus allowing clean, waste-free reactions. The scope is demonstrated by application of the protocol to a series allylic alcohols and vinyl arenes, leading to variety of 1,4-diene products. Based on kinetic studies, a mechanism is proposed that involves a palladium hydride species that activates the allyl alcohol to form the allyl intermediate.

摘要

描述了通过使用含亚磷酰胺配体的钯催化剂对烯丙醇进行直接脱水活化并随后与烯烃进行交叉偶联的过程。烯丙醇的活化不需要化学计量的添加剂,从而实现清洁、无废物的反应。通过将该方法应用于一系列烯丙醇和乙烯基芳烃,展示了其适用范围,得到了多种1,4 - 二烯产物。基于动力学研究,提出了一种涉及氢化钯物种的机理,该物种活化烯丙醇以形成烯丙基中间体。

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