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(±)-Hongoquercin A全合成:可见光促进有机催化多烯环化策略
  • ISSN号:0567-7351
  • 期刊名称:《化学学报》
  • 时间:0
  • 分类:O629.9[理学—有机化学;理学—化学]
  • 作者机构:中国科学院化学研究所分子识别与功能院重点实验室,北京100190
  • 相关基金:科技部(No.2012CB821600); 国家自然科学基金(Nos.21390400,21521002)资助; 中组部拔尖人才计划的支持~~
中文摘要:

报道了天然产物分子(±)-Hongoquercin A的仿生全合成路线.作者最近开发了在可见光促进下以染料分子曙红为光敏剂的自由基多烯环化反应.以此为基础,将该方法学应用于(±)-Hongoquercin A全合成中的关键步,一步构建该天然产物分子的多环骨架结构,共7步实现了其全合成.

英文摘要:

Advances in the strategy and methodology of visible light photocatalysis have begun to alter the way how organic chemists address the synthetic problems. These powerful methods have enabled the development of novel reaction schemes and approaches (mostly via radical path) for the total synthesis of nature products under visible light photoredox catalysis. Terpenoids, possessing intriguing biological activities together with their structural diversity, have remained as attractive targets for chemists. On the basis of their biogenetic pathways, polyene cyclization is the most straightforward pathway to attain terpenoid skeletons. Most recently, a few examples of stereoselective radical polyene cyclizations have been developed. However, most of the radical approaches suffer from the requirement for stoichiometric loading of metals or radical initiators. And in many cases, low yields are obtained with complicated reaction mixtures, which cumber further development along this line especially in nature products synthesis. In our previous work, we have developed a visible-light-mediated, stereose- lective organocatalytic cyclization of polyenes. The wide scope as well as the high chemoselectivity inspires us to apply this method in the total synthesis of terpenoid natural products. Thus we report here total synthesis of (+)-Hongoquercin A (1), starting from trans, trans-farnesol (4) in 7 steps and with overall 14.4% yield. Our developed visible-light-mediated redox organocatalytic methodology is employed as the key step to construct multiple ring-fused skeleton of I in one step. [To a flame-dried Schlenk tube equipped with a magnetic stir bar was added 3-hydroxy-5-methyl-2-((2E,6E)-3,7,11-trimethyl- dodeca-2,6,10-trien-l-yl)cyclohex-2-enone (3) (0.20 g, 0.61 mmol) and Eosin Y (4.0 mg, 0.0061 mmol). The mixture was diluted with 1.5 mL of anhydrous hexafluoroisopropanol. The reaction was irradiated with Green LEDs at room temperature for 2 h. Upon completion, the reaction mixture was

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期刊信息
  • 《化学学报》
  • 北大核心期刊(2014版)
  • 主管单位:中国科学院
  • 主办单位:中国化学会 中国科学院上海有机化学研究所
  • 主编:周其林
  • 地址:上海市零陵路345号
  • 邮编:200032
  • 邮箱:hxxb@sioc.ac.cn
  • 电话:021-54925085
  • 国际标准刊号:ISSN:0567-7351
  • 国内统一刊号:ISSN:31-1320/O6
  • 邮发代号:4-209
  • 获奖情况:
  • 首届国家期刊奖,第二届国家期刊奖提名奖,中国期刊方阵“双高期刊”
  • 国内外数据库收录:
  • 俄罗斯文摘杂志,美国化学文摘(网络版),荷兰文摘与引文数据库,美国科学引文索引(扩展库),日本日本科学技术振兴机构数据库,中国中国科技核心期刊,中国北大核心期刊(2004版),中国北大核心期刊(2008版),中国北大核心期刊(2011版),中国北大核心期刊(2014版),英国英国皇家化学学会文摘,中国北大核心期刊(2000版)
  • 被引量:28694