防风中亥茅酚及亥茅酚苷的不对称合成  

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

作　　者：曾涛 张曙盛 付建国 冯陈国 Zeng Tao;Zhang Shusheng;Fu Jianguo;Feng Chenguo(Innovation Research Institute of Traditional Chinese Medicine,Shanghai University of Traditional Chinese Medicine,Shanghai 201203)

机构地区：[1]上海中医药大学创新中药研究院,上海201203

出　　处：《有机化学》2024年第9期2862-2868,共7页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(Nos.22271195,22301185);上海市科学技术委员会(Nos.21ZR1482100,22ZR1458900);上海市中央引导地方科技发展资金(No.YDZX20223100001004);上海中医药大学有组织科研计划(No.2023YZZ01);上海中医药大学预算内(No.2021LK001)资助项目.

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.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.

关 键 词：防风 色原酮 亥茅酚 亥茅酚苷 不对称合成 

分 类 号：TQ460.31[化学工程—制药化工]