Simple and Efficient Synthesis of Pseudoginsenoside HQ

doi:10.6023/cjoc201703006

Chin. J. Org. Chem. ›› 2017, Vol. 37 ›› Issue (6): 1530-1536.DOI: 10.6023/cjoc201703006 Previous Articles Next Articles

Notes

拟人参皂苷HQ的简明高效合成

杨刚强, 李阳, 杨青, 岳馨, 姚雷, 姜永涛

烟台大学新型制剂与生物技术药物研究山东省高校协同创新中心分子药理和药物评价教育部重点实验室(烟台大学) 烟台 264005

收稿日期:2017-03-02 修回日期:2017-04-07 发布日期:2017-05-02
通讯作者: 杨刚强,姜永涛 E-mail:oceanygq@hotmail.com;yongtao@luye.cn
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

Yang Gangqiang, Li Yang, Yang Qing, Yue Xin, Yao Lei, Jiang Yongtao

School of Pharmacy, Collaborative Innovation Center of Advanced Drug Delivery System and Biotech Drugs in Universities of Shandong, Key Laboratory of Molecular Pharmacology and Drug Evaluation (Yantai University), Ministry of Education, Yantai University, Yantai 264005

Received:2017-03-02 Revised:2017-04-07 Published:2017-05-02
Contact: 10.6023/cjoc201703006 E-mail:oceanygq@hotmail.com;yongtao@luye.cn
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).

1. Simple and Efficient Synthesis of Pseudoginsenoside HQ.PDF(988KB)

Abstract

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.

Key words: pseudoginsenoside HQ, glycosylation, ocotillol type ginsenoside, chemical synthesis

Cite this article

Yang Gangqiang, Li Yang, Yang Qing, Yue Xin, Yao Lei, Jiang Yongtao. Simple and Efficient Synthesis of Pseudoginsenoside HQ[J]. Chin. J. Org. Chem., 2017, 37(6): 1530-1536.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

References

[1] (a) Si, J. G.; Tian, C. E. Lishizhen Med. Mater. Med. Res. 2016, 27, 1190 (in Chinese).(司建功, 田长恩, 时珍国医国药, 2016, 27, 1190.)
(b) Yang, Z. Q.; Zhao, T. T.; Liu, H. L.; Zhang L. D. Sci. Rep. 2016, 6, 19383.
(c) Li, B. H.; Zhao, J. O.; Wang, C. Z.; Searle, J.; He, T. C.; Yuan, C. S.; Du, W. Cancer Lett. 2011, 301, 185.
[2] Zhang, J. W.; Zhou, F.; Wu, X. L.; Zhang, X. X.; Chen, Y. C.; Zha, B. S.; Niu, F.; Lu, M.; Hao, G.; Sun, Y.; Sun, J. G.; Peng, Y.; Wang, G. J. Br. J. Pharmacol. 2012, 165, 120.
[3] Yang, J. Ph.D. Dissertation, Jilin University, Changchun, 2016 (in Chinese)(杨洁, 博士论文, 吉林大学, 长春, 2016.)
[4] Li, L.; Chen, X. Y.; Zhou, J. L.; Zhong, D. F. Drug Metab. Dispos. 2012, 40, 2041.
[5] Yang, J.; Li, X. W.; Sun, T.; Gao, Y.; Chen, Y. X.; Jin, Y. R.; Li, Y. Steroids 2016, 106, 26.
[6] Liu, J. Ph.D. Dissertation, Shenyang Pharmaceutical University, Shenyang, 2016 (in Chinese).(刘金平, 博士论文, 沈阳药科大学, 沈阳, 2005.)
[7] Shen, R. Z.; Xin, C.; Laval, S.; Sun, J. S.; Yu, B. J. Org. Chem. 2016, 81, 10279.
[8] Yang, N.; Yang, S. L.; Zhao, Y. Q. Drugs Clinic 2014, 29, 574 (in Chinese)(杨宁, 杨世林, 赵余庆, 现代药物与临床, 2014, 29, 574.)
[9] Liao, J. X.; Sun, J. S.; Niu, Y. M.; Yu, B. Tetrahedron Lett. 2011, 52, 3075.
[10] (a) Atopkina, L. N. Uvarova, N. I. Chem. Nat. Compd. 1981, 17, 254.
(b) Samoshina, N. F.; Novikov, V. L.; Denisenko, V. A.; Uvarova, N. I. Chem. Nat. Compd. 1983, 19, 299.
(c) Atopkina, L. N.; Novikov, V. L.; Denisenko, V. A.; Uvarova, N. I. Chem. Nat. Compd. 1985, 21, 674.
(d) Atopkina, L. N.; Uvarova, N. I. Chem. Nat. Compd. 1986, 22, 421.
(e) Atopkina, L. N.; Samoshina, N. F.; Denisenko, V. A.; Pokhilo, N. D.; Uvarova, N. I. Chem. Nat. Compd. 1986, 22, 415.
[11] (a) Yosioka, I.; Yamauchi, H.; Kitagawa, I. Chem. Pharm. Bull. 1972, 20, 502.
(b) Appendino, G.; Gariboldi, P.; Wollenweber, E. Sironi, A.; Molinari, H. Phytochemistry 1992, 31, 923.
(c) Bi, Y.; Tian, J. W.; Wang, L.; Zhao, F. L.; Zhang, J. F.; Wang, N.; Sun, H. J.; Meng, Q. G. J. Med. Plant. Res. 2011, 5, 2424.
(d) Li, L.; Chen, X. Y.; Li, D.; Zhong, D. F. Drug Metab. Dispos. 2011, 39, 472.
[12] Ren Y. Y. M.S. Thesis, Jilin University, Changchun, 2012 (in Chinese).(任媛媛, 硕士论文, 吉林大学, 长春, 2012.)
[13] Meng, Q. G.; Tan, W. J.; Hou, G. G.; Zhang, X. Y.; Hu, X. Y.; Yang, F.; Bai, G. J.; Zhu, W. W.; Cai, Y.; Bi, Y. J. Mol. Struct. 2013, 1054–1055, 1.
[14] Ueda, M.; Yang, G. Q.; Ishimaru, Y.; Itabashi, T.; Tamura, S.; Kiyota, H.; Kuwahara, S.; Inomata, S.; Shoji, M.; Sugai, T. Bioorg. Med. Chem. 2012, 20, 5832.
[15] Li, Y.; Yang, X. Y.; Liu, Y. P.; Zhun, C. S.; Yang, Y.; Yu, B. Chem.-Eur. J. 2010, 16, 1871.

拟人参皂苷HQ的简明高效合成

Simple and Efficient Synthesis of Pseudoginsenoside HQ

PDF

Supporting Info.

Knowledge

Cited

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Jingrui Wang, Yongkui Feng, Nengzhong Wang, Nianyu Huang, Hui Yao. Pd-Catalyzed Stereoselective Synthesis of Nitroalkyl β-C-Glycosides [J]. Chinese Journal of Organic Chemistry, 2023, 43(9): 3216-3225.
[2]	Dandan Sui, Nannan Cen, Ruoqu Gong, Yang Chen, Wenbo Chen. Supporting-Electrolyte-Free Electrochemical Synthesis of Trifluoromethylated Oxindoles in Continuous Flow [J]. Chinese Journal of Organic Chemistry, 2023, 43(9): 3239-3245.
[3]	Gefei Li, Jie Jing, Zhenyang Luo, Juan Mo, Decai Xiong, Xinshan Ye. Recent Advances in Protection-Free Glycosylations [J]. Chinese Journal of Organic Chemistry, 2023, 43(6): 1991-2001.
[4]	Junying Zhang, Xiaojing Zhao, Ganpeng Li, Yonghui He. Electrochemical Synthesis of Masked Organoboronic Acids RB(dan) at Room Temperature [J]. Chinese Journal of Organic Chemistry, 2023, 43(5): 1815-1823.
[5]	Yongzhou Pan, Xiujin Meng, Yingchun Wang, Muxue He. Recent Progress in Electrochemical Fixation of CO₂ to Construct Carboxylic Acid Derivatives [J]. Chinese Journal of Organic Chemistry, 2023, 43(4): 1416-1434.
[6]	Tianyang Wang, Yan-Mei Li. Progress on the Synthesis and Activity of Cyclic Dinucleotides as Stimulator of Interferon Gene (STING) Agonists [J]. Chinese Journal of Organic Chemistry, 2023, 43(3): 892-913.
[7]	Jiawei Huang, Xiaoman Li, Liang Xu, Yu Wei. Electrochemical Decarboxylation Coupling of α-Keto Acids with Thiophenols: A New Avenue for the Synthesis of Thioesters [J]. Chinese Journal of Organic Chemistry, 2023, 43(2): 756-762.
[8]	Haiqiong Li, Mengyun Yin, Fenfen Xie, Zhengbing Zhang, Pan Han, Linhai Jing. Synthesis of Nitrile via Electrochemical Appel Reaction [J]. Chinese Journal of Organic Chemistry, 2022, 42(7): 2229-2235.
[9]	Min Hua, Yangxing Sun, Xueqing Zhang, Hui Yao, Nianyu Huang. Convenient Cobalt-Catalyzed Stereoselective Synthesis of β-D-Thioglucosides [J]. Chinese Journal of Organic Chemistry, 2022, 42(7): 2140-2154.
[10]	Mengnan Lai, Qiuyuan Wang, Min Hua, Nianyu Huang, Hui Yao. Open-Air Stereoselective Synthesis of C-Aryl Fucosides/Arabinosides [J]. Chinese Journal of Organic Chemistry, 2022, 42(6): 1694-1705.
[11]	Zhengjiang Fu, Zhenjiang Yang, Li Sun, Jian Yin, Xuezheng Yi, Hu Cai, Aiwen Lei. Electrochemical Synthesis of Aryl Sulfonates from Sodium Sulfinates and Phenols under Metal-Free Conditions [J]. Chinese Journal of Organic Chemistry, 2022, 42(2): 600-606.
[12]	Xiaolong Guo, Yuxian Wang, Zhiqiang Zhao, Qing Wang, Jian Zuo, Luyao Wang. Electrochemical Oxidative C—H Trifluoromethylation of Quinoxalin-2(1H)-ones and the Performance Evaluation via Electro-descriptors [J]. Chinese Journal of Organic Chemistry, 2022, 42(2): 641-649.
[13]	Yangxing Sun, Yanzhi Li, Yanlai Cao, Nengzhong Wang, Shaohua Xiang, Mingguo Liu, Hui Yao. Research Advances in Functional Group-Directed Stereoselective Glycosylation [J]. Chinese Journal of Organic Chemistry, 2022, 42(11): 3506-3529.
[14]	Hongxia Li, Peng Chen, Zhilin Wu, Yuhan Lu, Junmei Peng, Jingyang Chen, Weimin He. Electrochemical Oxidative Cross-Dehydrogenative Coupling of Five-Membered Aromatic Heterocycles with NH₄SCN [J]. Chinese Journal of Organic Chemistry, 2022, 42(10): 3398-3404.
[15]	Zhiheng Zhao, Ming Li, Yaqin Zhou, Yonghui He, Lizhu Zhang, Ganpeng Li, Lijun Gu. Synthesis of 1,2,4-Triazoles via the Electrochemical Oxidative [3+2] Annulation [J]. Chinese Journal of Organic Chemistry, 2021, 41(6): 2476-2484.