有机化学 ›› 2018, Vol. 38 ›› Issue (7): 1663-1672.DOI: 10.6023/cjoc201712014 上一篇    下一篇

研究论文

无过渡金属催化2-重氮-3,5-二氧代-6-炔酯/炔酮/炔酰胺的区域选择性逆转环化:重氮γ-吡喃酮和重氮3(2H)-呋喃酮衍生物的合成

陆声乐, 涂现侠, 刘为顺, 沈利亭, 毛善检, 邓桂胜   

  1. 湖南师范大学 化学生物学与中药分析教育部重点实验室 长沙 410081;湖南师范大学 有机功能分子组装与应用重点实验室 长沙 410081
  • 收稿日期:2017-12-07 修回日期:2018-03-06 发布日期:2018-04-12
  • 通讯作者: 邓桂胜 E-mail:gsdeng@hunnu.edu.cn
  • 基金资助:

    国家自然科学基金(No.21372071)及湖南省自然科学基金(No.2016JJ2080)资助项目.

Transition Metal-Free-Catalyzed Regioselective Reversal in the Cyclization of 2-Diazo-3,5-dioxo-6-ynoates/ynones/ynamide: Synthesis of Diazo γ-Pyrones and Diazo 3(2H)-Furanones

Lu Shengle, Tu Xianxia, Liu Weishun, Shen Liting, Mao Shanjian, Deng Guisheng   

  1. Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research, Ministry of Education, Hunan Normal University, Changsha 410081;Key Laboratory of the Assembly and Application of Organic Functional Molecules, Hunan Normal University, Changsha 410081
  • Received:2017-12-07 Revised:2018-03-06 Published:2018-04-12
  • Contact: 10.6023/cjoc201712014 E-mail:gsdeng@hunnu.edu.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21372071) and the Hunan Provincial Natural Science Foundation (No. 2016JJ2080).

在六氟锑酸/乙醇的体系中,80℃条件下,2-重氮-3,5-二氧代-6-炔酯/炔酮/炔酰胺环化生成重氮γ-吡喃酮衍生物;然而,在乙酸/三乙胺/1,2-二氯乙烷体系中,25℃条件下,其环化反应主要生成重氮3(2H)-呋喃酮.在Rh(Ⅱ)催化下,这些重氮化合物与烯烃可以进行有效的分子间环丙烷化.

关键词: 重氮g-吡喃酮, 重氮3(2H)-呋喃酮, 合成, 环丙烷化, 区域选择性

For HSbF6/EtOH system, diazo γ-pyrones were cleanly obtained starting from 2-diazo-3,5-dioxo-6-ynoates/ynones/ynamide at 80℃, whereas diazo 3(2H)-furanones were predominantly generated in HOAc-Et3N-1,2-dichloroethane system at 25℃. These diazo compounds can undergo an efficient Rh(Ⅱ)-catalyzed intermolecular cyclopropanation with alkene.

Key words: diazo γ-pyrone, diazo 3(2H)-furanone, synthesis, cyclopropanation, regioselectivity