有机化学 ›› 2018, Vol. 38 ›› Issue (11): 2993-3001.DOI: 10.6023/cjoc201804048 上一篇    下一篇

所属专题: 有机小分子-金属协同催化

研究论文

焦脱镁叶绿酸与重氮烷的重排反应及其叶绿素衍生物的合成

张珠a, 徐希森b, 李彦龙b, 李家柱b, 王进军a,b   

  1. a 烟台大学文经学院食品与生物工程系 烟台 264005;
    b 烟台大学化学化工学院 烟台 264005
  • 收稿日期:2018-04-30 修回日期:2018-06-16 发布日期:2018-07-24
  • 通讯作者: 王进军 E-mail:wjj1955@163.com
  • 基金资助:

    国家自然科学基金(No.21272048)和山东省高校科技计划(No.J15LC51)资助项目.

Rearrangement Reactions of Pyropheophorbide with Diazoalkane and Synthesis of Chlorophyll Derivatives

Zhang Zhua, Xu Xisenb, Li Yanlongb, Li Jiazhub, Wang Jinjuna,b   

  1. a Department of Food & Biological Engineering, Wenjing College, Yantai University, Yantai 264005;
    b College of Chemistry and Chemical Engineering, Yantai University, Yantai 264005
  • Received:2018-04-30 Revised:2018-06-16 Published:2018-07-24
  • Supported by:

    Project supported by the National Natural Science Foundations of China (No. 21272048) and the University Science and Technology Plan Projects of Shandong Province (No. J15LC51).

以焦脱镁叶绿酸-a甲酯及其N21-N23轴向酰化和烯化的衍生物为起始原料,环上碳碳双键或碳氧双键与重氮烷发生1,3-偶极环加成、Michael加成和Tiffeneau-Demjanov重排反应,在周环上的不同位置上形成新的杂环和羰基结构,完成了一系列未见报道的叶绿素类二氢卟吩衍生物的合成.同时,基于相应的反应机理,讨论了重排过程的区域和立体选择性.

关键词: 叶绿素-a, 二氢卟吩, 焦脱镁叶绿酸, 重氮烷, 重排反应

Pyropheophorbide-a methyl ester and its derivatives acidylated and alkenylated along the N21-N23 axis were used as starting materials. The 1,3-dipolar cyclocaddition, Michael addition and Tiffeneau-Demjanov rearrangement reaction can smoothly occur with diazoalkane through the carbon-oxygen or carbon-carbon double bonds attached to the periphery to generate new heterocyclic and carbonylic structures in different positions. The synthesis of a series of unreported chlorins related to chlorophyll was accomplished and their chemical structures were characterized by elemental analysis, UV-Vis, IR, MS and 1H NMR spectra. Meanwhile, the region-and stereo-selectivities of rearrangement processes were discussed based on relevant reaction mechanism.

Key words: chlorophyll-a, chlorin, pyropheophorbide, diazoalkane, rearrangement reaction