铜催化炔基溴与丙炔醇的偶联-异构化反应合成戊炔烯酮(封面文章)

doi:10.6023/cjoc201411017

有机化学 ›› 2015, Vol. 35 ›› Issue (3): 610-617.DOI: 10.6023/cjoc201411017 上一篇下一篇

研究论文

铜催化炔基溴与丙炔醇的偶联-异构化反应合成戊炔烯酮(封面文章)

杨宗莲^a, 廖沛球^a, 李兴奇^a, 毕锡和^a,b

a 东北师范大学化学学院长春 130024;
b 南开大学元素有机化学国家重点实验室天津 300071

收稿日期:2010-11-10 修回日期:2014-12-16 发布日期:2014-12-18
通讯作者: 毕锡和 E-mail:bixh507@nenu.edu.cn
基金资助:
国家自然科学基金(Nos. 21172029, 21202016, 21372038)资助项目.

Pentynenones Formation through Copper Catalyzed Coupling- Isomerization Reaction between Alkynyl Bromides and Propargylic Alcohols

Yang Zonglian^a, Liao Peiqiu^a, Li Xingqi^a, Bi Xihe^a,b

a Department of Chemistry, Northeast Normal University, Changchun 130024;
b State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071

Received:2010-11-10 Revised:2014-12-16 Published:2014-12-18
Supported by:
Project supported by the National Natural Science Foundation of China (Nos. 21172029, 21202016, 21372038).

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摘要/Abstract

乙炔溴和丙炔醇在哌啶溶剂中, 用醋酸铜作催化剂, 能够发生偶联-异构化反应获得具有立体选择性的唯一产物(E)-1,5-二取代-戊-2-烯-4-炔-1-酮. 机理研究表明, 哌啶在反应体系中起到了溶剂和碱的双重作用. 该反应具有简单、高效、反应范围宽泛等特点, 能够以40%～83%的产率获得目标产物反式1,5-二取代的戊炔烯酮.

关键词: 戊炔烯酮, 乙炔溴, 丙炔醇, 偶联-异构化反应

1,5-Disubstituted (E)-pent-2-en-4-yn-1-ones can be exclusively synthesized by copper-catalyzed tandem coupling-isomerization reaction of alkynyl bromides and secondary propargylic alcohols in piperidine. This method is operation-simple and allows the synthesis of a wide variety of stereodefined 1,5-disubstituted pentynenones in 40%～83% yields. The mechanistic investigations suggest that piperidine plays a duel role being both a solvent and a base in the reaction.

Key words: pentynenones, alkynyl bromides, propargylic alcohols, coupling-isomerization reaction

引用此文

杨宗莲, 廖沛球, 李兴奇, 毕锡和. 铜催化炔基溴与丙炔醇的偶联-异构化反应合成戊炔烯酮(封面文章)[J]. 有机化学, 2015, 35(3): 610-617.

Yang Zonglian, Liao Peiqiu, Li Xingqi, Bi Xihe. Pentynenones Formation through Copper Catalyzed Coupling- Isomerization Reaction between Alkynyl Bromides and Propargylic Alcohols[J]. Chin. J. Org. Chem., 2015, 35(3): 610-617.

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铜催化炔基溴与丙炔醇的偶联-异构化反应合成戊炔烯酮(封面文章)

Pentynenones Formation through Copper Catalyzed Coupling- Isomerization Reaction between Alkynyl Bromides and Propargylic Alcohols

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