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2024 , Vol. 44 >Issue 9: 2862 - 2868

DOI: https://doi.org/10.6023/cjoc202403006

研究论文

防风中亥茅酚及亥茅酚苷的不对称合成

  • 曾涛 ,
  • 张曙盛 ,
  • 付建国 ,
  • 冯陈国
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  • 上海中医药大学创新中药研究院 上海 201203

收稿日期: 2024-03-04

  修回日期: 2024-04-15

  网络出版日期: 2024-05-17

基金资助

国家自然科学基金(22271195); 国家自然科学基金(22301185); 上海市科学技术委员会(21ZR1482100); 上海市科学技术委员会(22ZR1458900); 上海市中央引导地方科技发展资金(YDZX20223100001004); 上海中医药大学有组织科研计划(2023YZZ01); 及上海中医药大学预算内(2021LK001)

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Asymmetric Synthesis of Hamaudol and sec-O-Glucosylhamaudol in Saposhnikovia divaricata (Turcz.) Schischk

  • Tao Zeng ,
  • Shusheng Zhang ,
  • Jianguo Fu ,
  • Chenguo Feng
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  • Innovation Research Institute of Traditional Chinese Medicine, Shanghai University of Traditional Chinese Medicine, Shanghai 201203
*E-mail: ;

Received date: 2024-03-04

  Revised date: 2024-04-15

  Online published: 2024-05-17

Supported by

National Natural Science Foundation of China(22271195); National Natural Science Foundation of China(22301185); Science and Technology Commission of Shanghai Municipality(21ZR1482100); Science and Technology Commission of Shanghai Municipality(22ZR1458900); Shanghai Science and Technology Development Fund from Central Leading Local Government(YDZX20223100001004); Organizational Key R&D Program of Shanghai University of Traditional Chinese Medicine(2023YZZ01); Expenditure Budget Program of Shanghai University of Traditional Chinese Medicine(2021LK001)

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摘要

色原酮类化合物作为中药防风中的主要成分具有广泛的生物活性, 其中代表性化合物亥茅酚和亥茅酚苷分别具有抗过敏和抗炎活性. 报道了一条亥茅酚及亥茅酚苷的不对称合成路线, 该路线主要利用Ca(OH)2促进酚烯醇与异戊烯醛发生aldol/环化串联反应, 高区域选择性地构建6/6/6三环核心骨架, 利用Jacobsen不对称环氧化反应实现3'位手性中心的构建, 以线性6步21%总收率实现亥茅酚的不对称合成, 以线性8步15%总收率完成了亥茅酚苷的不对称合成.

关键词： 防风; 色原酮; 亥茅酚; 亥茅酚苷; 不对称合成

本文引用格式

曾涛 , 张曙盛 , 付建国 , 冯陈国 . 防风中亥茅酚及亥茅酚苷的不对称合成[J]. 有机化学, 2024 , 44(9) : 2862 -2868 . DOI: 10.6023/cjoc202403006

Abstract

Chromones from the traditional Chinese medicine Saposhnikovia divaricata (Turcz.) Schischk exhibit various biological activities, among which the representative compounds, hamaudol and sec-O-glucosylhamaudol, have anti-allergic and anti-inflammatory activities. A concise asymmetric synthesis of hamaudol and sec-O-glucosylhamaudol has been accomplished. The key strategies included the Ca(OH)2-catalyzed regioselective construction of 6/6/6 tricyclic skeleton by aldol reaction/annulation of phenolic enolate with 3-methyl-2-butenal and the construction of chiral centers in the 3'-position by Jacobsen's asymmetric epoxidation reaction. This strategy provided a concise and rapid approach to synthesize hamaudol (linear 6-steps and 21% overall yield) and sec-O-glucosylhamaudol (linear 8-steps and 15% overall yield) from the commercial reagent.

Key words： Saposhnikovia Divaricata (Turcz.) schischk; chromone; hamaudol; sec-O-glucosylhamaudol; asymmetric synthesis

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