天然孕甾烷-17(20)-烯中C-17位双键构型的快速测定

波谱学杂志 ›› 2011, Vol. 28 ›› Issue (1): 93-98.

天然孕甾烷-17(20)-烯中C-17位双键构型的快速测定

江海鹏^1,2，蒋先旺^1,2，张许^1*，刘买利¹

1. State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Center of Magnetic Resonance, (Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences), Wuhan 430071, China;
2. Graduate School of the Chinese Academy of Sciences, Beijing 100049, China

收稿日期:2010-04-01 修回日期:2010-04-15 出版日期:2011-03-05 发布日期:2011-03-05
基金资助:
国家自然科学基金资助项目（20875098），武汉市晨光计划资助项目（200850731401）.

Rapid Configuration Determination of Carbon-17Ethylene Bond in Natural Pregn-17(20)-ene

JIANG Hai-Peng^1,2, JIANG Xian-Wang^1,2, ZHANG Xu^1*, LIU Mai-Li¹

Received:2010-04-01 Revised:2010-04-15 Online:2011-03-05 Published:2011-03-05
Supported by:
国家自然科学基金资助项目（20875098），武汉市晨光计划资助项目（200850731401）.

摘要/Abstract

摘要：

天然孕甾烷-17(20)-烯中C-17位双键的构型对分子的药理性质有重要的影响，但是采用化学位移比较等方法判断其构型存在费时以及区分模糊等缺点. 该文以E-和Z-guggulsterone为模型化合物，利用一维选择性NOE实验来进行天然孕甾烷-17(20)-烯中C-17位双键的构型测定. 由于空间相对位置受到构型影响，选择反转20位的质子时，如果选择性NOE谱中仅能检测到21位甲基氢，表明该化合物为E-构型；如果除了21位甲基氢外，18位甲基氢和12位氢也存在于选择性NOE谱中，则表明该化合物为Z-构型. 实验结果表明该方法具有区分度大，简单快速等优点，可以普遍适用于这些孕甾烷类化合物17位双键构型的确定.

关键词: 核磁共振(NMR), 构型, 选择性NOE, 孕甾烷-17(20)-烯

Abstract:

The configuration of carbon-17 ethylene bond in pregn-17(20)-ene derivatives has important influence on the pharmacological properties of the compounds. However, the previously used methods for configuration determination of pregn-17(20)-ene derivatives either are time consuming or cannot obtain certain results. In this paper, we proposed to use 1D selective NOESY to determine the configuration of carbon-17 ethylene bond in E- and Z-guggulsterone. The results showed that, by selective inversion of H-20, the NOE spectra of E-guggulsterone showed only the signal from H-21, while that of Z-guggulsterone showed additional signals from H-18 and H-12. Our results indicated that the selective NOE experiment is a rapid and simple method for configuration determination of the carbon-17 ethylene bond in pregnanes.

Key words: NMR, configuration, selective NOESY, pregn-17(20)-ene

中图分类号:

O482.53

江海鹏, 蒋先旺, 张许, 刘买利. 天然孕甾烷-17(20)-烯中C-17位双键构型的快速测定[J]. 波谱学杂志, 2011, 28(1): 93-98.

JIANG Hai-Peng, JIANG Xian-Wang, ZHANG Xu, LIU Mai-Li. Rapid Configuration Determination of Carbon-17Ethylene Bond in Natural Pregn-17(20)-ene[J]. Chinese Journal of Magnetic Resonance, 2011, 28(1): 93-98.

参考文献

[1] Brobst D E, Ding X S, Creech K L, et al. Guggulsterone activates multiple nuclear receptors and induces CYP3A gene expression through the pregnane X receptor[J]. Journal of Pharmacology and Experimental Therapeutics, 2004, 310: 528-535.

[2] Joycharat N, Greger H, Hofer, et al. Flavaglines and triterpenoids from the leaves of Aglaia forbesii[J]. Phytochemistry, 2008, 69: 206-211.

[3] Hung T, Stuppner H, Ellmerermuller E P, et al. Steroids andterpenoids from the gum resin of Ailanthus grandis[J]. Phytochemistry, 1995, 39: 1 403-1 409.

[4] Atta ur R, Choudhary M I, Shaheen F, et al. Microbial transformations of hypolipemic E-guggulsterone[J]. Journal of Natural Products, 1998, 61(4): 428-431.

[5] Peakman T M, Maxwell J R. Acid-catalysed rearrangements of steroid alkenes. Part 1. Rearrangement of 5-cholest-7-ene[J]. Journal of the Chemical Society-Perkin Transactions 1, 1988, 1 065-1 070.

[6] Kessler H, Oschkinat H, Griesinger C. Transformation of homonuclear two-dimensional NMR techniques intoone-dimensional techniques using Gaussian pulses[J]. J Magn Reson, 1986, 70: 106-133.

[7] Zhao Yu-mei(赵玉梅), Liu Li-jun(刘力军), Miao Zhen-chun(缪振春). Structural determination of an aglycome by long-range DEPT and selective NOESY techniques(选择性远程DEPT和选择性NOESY技术用于苷类化合物的结构研究)[J]. Chinese J Magn Reson(波谱学杂志), 2008, 25(3): 342-348.

[8] Urizar N L, Liverman A B, Dodds D T, et al. A natural product that lowers cholesterol as an antagonist ligand for FXR[J]. Science, 2002, 296: 1 703-1 706.

[9] Lei Lian-di(雷连娣), Liu Xue-hui(刘雪辉), Jin Yun(金赟), et al. Characterization of the terminal aikyne group in a key intermediate of cephalotaxine by NMR spectroscopy(三尖杉碱骨架构筑中间体末端炔键的NMR确证)[J]. Chinese J Magn Reson(波谱学杂志), 2008, 25(1): 46-52.

[10] Benn W R, Dodson R M. The synthesis and stereochemistry of isomeric 16-Hydroxy-17(20)-pregnenes[J]. J Org Chem, 1964, 29(5): 1 142-1 148.

[11] Plaza A, Piacente S, Perrone A, et al. Stemmosides C and D, two novel unusual pregnane glycosides from Solenostemma angel: structural elucidation and configurational study by a combined NMR-quantum mechanical strategy[J]. Tetrahedron, 2004, 60: 12 201-12 209.

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