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)有机化学.pdfVIP

DOI: 10.6023/cjoc201411017 研究论文 有机化学 Chinese Journal of Organic Chemistry ARTICLE 铜催化炔基溴与丙炔醇的偶联-异构化反应合成戊炔烯酮 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) 摘要 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 Pentynenones Formation through Copper Catalyzed Coupling- Isomerization Reaction between Alkynyl Bromides and Propargylic Alcohols Yang, Zongliana Liao, Peiqiua Li, Xingqia 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) Abstract 1,5-Disubstituted (E)-pent-2-en-4-yn-1-ones can be exclusively synthesized by copper-catalyzed tandem cou- pling-isomerization reaction of alkynyl bromides and secondary propargylic alcohols in piperidine. This method is opera- tion-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. Keywords pentynenones; alkynyl bromides; propargylic alcohols; coupling-isomerization reaction 戊炔烯酮是含有共轭 C≡C, C ＝C 和 C ＝O 键的一 类化合物[6～9]. 如图 1 所示, 所用方法