有机化学 ›› 2018, Vol. 38 ›› Issue (9): 2324-2334.DOI: 10.6023/cjoc201805059 上一篇    下一篇

所属专题: 合成科学

综述与进展

天然产物中环丙烷官能团的构筑策略

金文兵, 袁华, 唐功利   

  1. 中国科学院上海有机化学研究所 生命有机化学国家重点实验室 上海 200032
  • 收稿日期:2018-05-31 修回日期:2018-06-26 发布日期:2018-07-24
  • 通讯作者: 唐功利 E-mail:gltang@sioc.ac.cn
  • 基金资助:

    国家自然科学基金(No.21502217)和上海市自然科学基金(No.15ZR1449400)资助项目.

Strategies for Construction of Cyclopropanes in Natural Products

Jin Wenbing, Yuan Hua, Tang Gongli   

  1. State Key Laboratory of Bio-organic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
  • Received:2018-05-31 Revised:2018-06-26 Published:2018-07-24
  • Contact: 10.6023/cjoc201805059 E-mail:gltang@sioc.ac.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21502217) and the Science and Technology Commission of Shanghai Municipality (No. 15ZR1449400).

环丙烷天然产物一般具有良好的生物活性,并且有着开发成先导药物的潜力.天然产物中环丙烷官能团环张力的存在使其化学合成和生物合成都富有极大的挑战性,但是由于这类化合物的重要性,环丙烷官能团的构筑无论是在化学合成还是在生物合成领域都取得了重要的进展.简要归纳和总结了化学合成和生物合成构筑环丙烷的策略.化学合成策略包括(i)卡宾的参与、(ii)分子内SN2反应和(iii)环异构化等.生物合成策略包括(i)碳正离子的参与、(ii)碳负离子的参与和(iii)碳自由基的参与.化学合成和生物合成是相互促进的,化学合成的策略可以指导科学家设计新的生化反应,而新的生化反应的发现也能启迪合成化学家设计新的合成路线.

关键词: 天然产物, 环丙烷, 化学合成, 生物合成, 催化机制

Cyclopropane-containing natural products frequently possess excellent biological activities, and may be developed as drug leads. Although the inherent strain of the cyclopropane greatly challenges both chemical synthesis and biosynthesis, great advances have been made for the construction of the cyclopropane in natural products by chemical synthesis owing to the importance of this kind of compounds. Many enzymes responsible for cyclopropanation have also been unraveled. This review summarizes the cyclopropanation strategies in chemical synthesis and biosynthesis. The strategies used in chemical synthesis mainly consist of three classes:(i) a carbene involved mechanism, (ii) an SN2 reaction mechanism, and (iii) cycloisomerization. The strategies discovered in nature are reviewed on the basis of the carbon state involved, including (i) a carbocation, (ii) a carbanion, and (iii) a carbon radical. Chemical synthesis and biosynthesis are mutually simulative because the strategies developed in chemical synthesis may inspire enzymologists to discover and design new biochemical reactions and vice versa.

Key words: natural products, cyclopropane, chemical synthesis, biosynthesis, catalytic mechanism