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烯丙基-钯催化羧酸通过烯醇化物的α,β-脱氢反应。

Allyl-Palladium-Catalyzed α,β-Dehydrogenation of Carboxylic Acids via Enediolates.

机构信息

Department of Chemistry, Yale University, 225 Prospect Street, PO Box 208107, New Haven, CT, 06511, USA.

Current address: School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Mei-Long Road, Shanghai, 200237, China.

出版信息

Angew Chem Int Ed Engl. 2017 Oct 9;56(42):13122-13125. doi: 10.1002/anie.201706893. Epub 2017 Sep 6.

DOI:10.1002/anie.201706893
PMID:28796936
Abstract

A highly practical and step-economic α,β-dehydrogenation of carboxylic acids via enediolates is reported through the use of allyl-palladium catalysis. Dianions underwent smooth dehydrogenation when generated using Zn(TMP) ⋅2 LiCl as a base in the presence of excess ZnCl , thus avoiding the typical decarboxylation pathway of these substrates. Direct access to 2-enoic acids allows derivatization by numerous approaches.

摘要

通过烯丙基钯催化,报道了一种高度实用且经济的羧酸通过烯醇化物的α,β-脱氢反应。当使用 Zn(TMP)·2LiCl 作为碱,并在过量 ZnCl 的存在下生成二阴离子时,二阴离子经历了顺利的脱氢,从而避免了这些底物的典型脱羧途径。直接得到 2-烯酸允许通过多种方法进行衍生化。

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