拟人参皂苷HQ的简明高效合成
收稿日期: 2017-03-02
修回日期: 2017-04-07
网络出版日期: 2017-05-02
基金资助
国家自然科学基金（No.21502164）、山东省优秀中青年科学家科研奖励基金（No.BS2015YY039）、烟台大学博士科研基金（No.YX14B17）资助项目.
Simple and Efficient Synthesis of Pseudoginsenoside HQ
Received date: 2017-03-02
Revised date: 2017-04-07
Online published: 2017-05-02
Supported by
Project supported by the National Natural Science Foundation of China (No. 21502164), the Research Fund for Excellent Young and Middle-age Scientists of Shandong Province (No. BS2015YY039), and the Startup Project of Doctor Scientific Research in Yantai University (No. YX14B17).
拟人参皂苷HQ （PHQ），化学名称3β-O-β-D-吡喃葡萄糖基-（20S，24S）-环氧达玛-12β，25-二醇，是一种生物活性较高的稀有人参皂苷Rh2在体内的主要代谢产物，具有潜在的药用价值.目前报道的合成线路复杂且总收率较低，是因为关键的苷元C-3位糖苷化需要合理的保护策略才能实现.通过奥克梯隆型皂苷元C-3位的糖苷化条件探索，首次发现以Ag2CO3为促进剂，免保护策略，即可实现苷元C-3位选择性糖苷化制备PHQ.从商品20（S）-原人参二醇出发，经氧化环化、选择性糖苷化和对糖基脱苯甲酰基保护三步完成PHQ的合成.本方法为PHQ及其衍生物的制备提供了一条简明高效途径.
杨刚强 , 李阳 , 杨青 , 岳馨 , 姚雷 , 姜永涛 . 拟人参皂苷HQ的简明高效合成[J]. 有机化学, 2017 , 37(6) : 1530 -1536 . DOI: 10.6023/cjoc201703006
Pseudoginsenoside HQ[PHQ, 3β-O-β-D-glucopyranosyl-(20S,24S)-epoxydammarane-12β,25-diol] is the main in vivo metabolite of 20(S)-ginsenoside Rh2 which has high biological activities, with potential medicinal value. The reported chemical synthesis of PHQ suffered complex synthetic route and low overall yield because the rational protecting group strategies were required for the key glycosylation on C-3 position of sapogenins. In this paper, the glycosylation conditions on C-3 position of ocotillol type sapogenins were investigated, and it was found that it could realize the selective glycosylation on C-3-position of sapogenins to prepare PHQ under the Ag2CO3 promoter without the protecting group strategy. A new synthesis of PHQ was achieved in three steps via epoxidation, selective glycosylation and debenzoylation reaction of glycon using commercially available 20(S)-protopanoxadiol as the starting material. This method provides a simple and efficient way for the preparation of PHQ and its derivatives.
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