自由基多烯环化反应在天然产物全合成中的应用  

Application of the Radical Polyene Cyclization Reaction in Natural Product Synthesis

作　　者：姚良才 桂敬汉 Liangcai Yao;Jinghan Gui(College of Chemistry and Materials Science,Shanghai Normal University,Shanghai 200233;CAS Key Laboratory of Synthetic Chemistry of Natural Substances,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,Shanghai 200032)

机构地区：[1]上海师范大学化学与材料科学学院,上海200233 [2]中国科学院上海有机化学研究所中国科学院天然产物有机合成化学重点实验室,上海200032

出　　处：《有机化学》2022年第9期2703-2714,共12页Chinese Journal of Organic Chemistry

基　　金：国家重点研发计划(No.2021YFF0502400);国家自然科学基金(Nos.22122112,21871289);上海市科学技术委员会(No.21ZR1476400);上海市扬帆计划(No.21YF1456400);国家中医药管理局多学科交叉创新团队(No.ZYYCXTD-202004)资助项目。

摘　　要：多环化合物普遍存在于天然产物、合成药物、农药化学品和精细化学品中,具有广泛的生物活性,因此如何高效合成多环化合物是有机合成的一个重要研究方向.近年来,多烯烃的自由基串联环化反应越来越成为构建多环骨架的一种可靠、简便途径,然而目前有关自由基串联环化方面的研究论文特别是近年来发展的环氧均裂开环引发自由基多烯环化反应并未被总结归纳.因此主要综述了自由基多烯环化反应的引发方法及其在多环天然产物合成中的应用,将着重介绍环氧多烯在Ti(III)作用下的自由基多烯串联环化反应.Polycyclic compounds, which exist widely in natural products, synthetic drugs, agrochemicals, fine chemicals, etc.have a wide range of biological activities. Therefore, efficient synthesis of polycyclic compounds is an important research direction in organic synthesis. In recent years, free radical cascade cyclization of polyenes has increasingly become a reliable and concise way to construct polycyclic skeletons. However, the research papers on free radical cascade cyclization, especially those initiated by the homolysis of epoxides, have not been summarized. Therefore, this paper mainly reviews the initiation methods of free radical polyene cascade cyclization and its application in the synthesis of polycyclic natural products, with an emphasis on the Ti(III)-mediated free radical cascade cyclization of polyene epoxides.

关 键 词：多环骨架 环氧多烯 自由基 串联环化 天然产物合成 

分 类 号：O629[理学—有机化学]