Citation: Shen Renzeng, Cao Xin, Yu Biao. Total Synthesis of Dammarane-Type Saponins Ginsenoside Re and Notoginsenoside R₁[J]. Acta Chimica Sinica, ;2018, 76(4): 278-285. doi: 10.6023/A17120544 shu

Total Synthesis of Dammarane-Type Saponins Ginsenoside Re and Notoginsenoside R₁

State Key Laboratory of Bio-organic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Corresponding author: Cao Xin, caoxin@sioc.ac.cn Yu Biao, byu@sioc.ac.cn
Received Date: 18 December 2017
Available Online: 7 April 2018
Fund Project: Project supported by the National Natural Science Foundation of China (Nos. 21432012, 21621002), the Strategic Priority Research Program of CAS (No.XDB20020000), Youth Innovation Promotion Association of CAS (No. 2017300) and the K. C. Wong Education Foundationthe National Natural Science Foundation of China 21432012Innovation Promotion Association of CAS 2017300the National Natural Science Foundation of China 21621002the Strategic Priority Research Program of CAS XDB20020000

Figures(3)

Ginsenoside Re (1) and Notoginsenoside R₁ (2) are two representative dammarane type protopanaxatriol-6, 20-O-bisglycosides occurring widely founded in Panaxginseng. Ginsenoside Re (1) showed potent antioxidative, anti-inflammatory and antihyperlipemia activities, and Notoginsenoside R₁ (2) showed potent antioxidative and antiinflammatory activities, so it would be helpful to synthesize these homogeneous natural products in appreciable amounts by accelerating their structure-activity relationship study. As a persistent effort on the chemical syntheses of the diverse ginsenosides in our group, we report herein the efficient syntheses of these two complex natural products. Thus, based on the reactivity sequence of the four hydroxyl groups (i.e., 12-OH > 3-OH > 6-OH >> 20-OH) of the protopanaxatriol aglycon, an orthogonal and efficient protecting group strategy was applied to distinguish these hydroxyl groups. The subsequent installation of the 6, 20-O-bisglycosides are challenging, given the poor reactivity of the secondary 6-OH and tertiary 20-OH, moreover, with the latter being labile toward acidic conditions. Taking advantage of the neutral conditions of the Au(Ⅰ)-catalyzed glycosylation reaction (0.3 equiv. Ph₃PAuNTf₂, 4 Å MS, CH₂Cl₂, r.t.), the glycosylation of the acid-labile 20-hydroxyl group was achieved effectively in a high 84% yield firstly. To be convergent for the syntheses of these two ginsenosides, the 6-O-disaccharide residues were installed in a stepwise manner. For the glycosylation of the 6-OH of protopanaxatriol, a higher loading of the catalyst Ph₃PAuNTf₂ (0.5 equiv.) was employed in order to increase the glycosylation yield while reduce the orthoester formation, thus, the desired 6β-O-glucosides were prepared in satisfactory yields (77%~83%). Both terminal α-L-Rha/β-D-Xyl moieties at the 2' position of 6-O-glc were installed efficiently under 0.2 equiv. Ph₃PAuNTf₂ catalyzing condition (ClCH₂CH₂Cl, 5 Å MS, 40℃) with 86% and 81% yields, respectively. After global deprotection, Ginsenoside Re (1) and Notoginsenoside R₁ (2) were synthesized with the longest 13 linear steps in 5.1% and 4.5% overall yields, respectively.
- dammarane-type saponin,
- Ginsenoside Re,
- Notoginsenoside R₁,
- Au (Ⅰ)-catalyzed glycosylation,
1. [1]
2. [2]
3. [3]
4. [4]
5. [5]
  Yu, J.; Sun, J.; Niu, Y.; Li, R.; Liao, J.; Zhang, F.; Yu, B. Chem. Sci. 2013, 4, 3899. doi: 10.1039/c3sc51479j
6. [6]
7. [7]
8. [8]
9. [9]
10. [10]
11. [11]
  Yang, W.; Sun, J.; Yang, Z.; Han, W.; Zhang, W.; Yu, B. Tetrahedron Lett. 2012, 53, 2773. doi: 10.1016/j.tetlet.2012.03.103
12. [12]
  Sun, J.; Han, X.; Yu, B. Synlett 2005, 3, 437.
13. [13]
  Liu, T.; Liao, J.; Hu, Y.; Tu, Y.; Sun, J. J. Org. Chem. 2017, 82, 4170. doi: 10.1021/acs.joc.7b00080
1. [1]
  Guangming YIN , Huaiyao WANG , Jianhua ZHENG , Xinyue DONG , Jian LI , Yi'nan SUN , Yiming GAO , Bingbing WANG . Preparation and photocatalytic degradation performance of Ag/protonated g-C₃N₄ nanorod materials. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1491-1500. doi: 10.11862/CJIC.20240086
2. [2]
  Yufang GAO , Nan HOU , Yaning LIANG , Ning LI , Yanting ZHANG , Zelong LI , Xiaofeng LI . Nano-thin layer MCM-22 zeolite: Synthesis and catalytic properties of trimethylbenzene isomerization reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1079-1087. doi: 10.11862/CJIC.20240036
3. [3]
  Hong LI , Xiaoying DING , Cihang LIU , Jinghan ZHANG , Yanying RAO . Detection of iron and copper ions based on gold nanorod etching colorimetry. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 953-962. doi: 10.11862/CJIC.20230370
4. [4]
  Shuo Zhang , Haitao Liao , Zhi-Qun Liu , Chong Yan , Jia-Qi Huang . Re-evaluating the nano-sized inorganic protective layer on Cu current collector for anode free lithium metal batteries. Chinese Chemical Letters, 2024, 35(7): 109284-. doi: 10.1016/j.cclet.2023.109284
5. [5]
  Tiantian MA , Sumei LI , Chengyu ZHANG , Lu XU , Yiyan BAI , Yunlong FU , Wenjuan JI , Haiying YANG . Methyl-functionalized Cd-based metal-organic framework for highly sensitive electrochemical sensing of dopamine. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 725-735. doi: 10.11862/CJIC.20230351
6. [6]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
7. [7]
  Kun WANG , Wenrui LIU , Peng JIANG , Yuhang SONG , Lihua CHEN , Zhao DENG . Hierarchical hollow structured BiOBr-Pt catalysts for photocatalytic CO₂ reduction. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1270-1278. doi: 10.11862/CJIC.20240037
8. [8]
  Zhanggui DUAN , Yi PEI , Shanshan ZHENG , Zhaoyang WANG , Yongguang WANG , Junjie WANG , Yang HU , Chunxin LÜ , Wei ZHONG . Preparation of UiO-66-NH₂ supported copper catalyst and its catalytic activity on alcohol oxidation. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 496-506. doi: 10.11862/CJIC.20230317
9. [9]
  Juan WANG , Zhongqiu WANG , Qin SHANG , Guohong WANG , Jinmao LI . NiS and Pt as dual co-catalysts for the enhanced photocatalytic H₂ production activity of BaTiO₃ nanofibers. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1719-1730. doi: 10.11862/CJIC.20240102
10. [10]
  Ruolin CHENG , Haoran WANG , Jing REN , Yingying MA , Huagen LIANG . Efficient photocatalytic CO₂ cycloaddition over W₁₈O₄₉/NH₂-UiO-66 composite catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 523-532. doi: 10.11862/CJIC.20230349
11. [11]
  Yi YANG , Shuang WANG , Wendan WANG , Limiao CHEN . Photocatalytic CO₂ reduction performance of Z-scheme Ag-Cu₂O/BiVO₄ photocatalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 895-906. doi: 10.11862/CJIC.20230434
12. [12]
  Zhiwen HU , Weixia DONG , Qifu BAO , Ping LI . Low-temperature synthesis of tetragonal BaTiO₃ for piezocatalysis. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 857-866. doi: 10.11862/CJIC.20230462
13. [13]
  Guimin ZHANG , Wenjuan MA , Wenqiang DING , Zhengyi FU . Synthesis and catalytic properties of hollow AgPd bimetallic nanospheres. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 963-971. doi: 10.11862/CJIC.20230293
14. [14]
  Kai CHEN , Fengshun WU , Shun XIAO , Jinbao ZHANG , Lihua ZHU . PtRu/nitrogen-doped carbon for electrocatalytic methanol oxidation and hydrogen evolution by water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1357-1367. doi: 10.11862/CJIC.20230350
15. [15]
  Juntao Yan , Liang Wei . 2D S-Scheme Heterojunction Photocatalyst. Acta Physico-Chimica Sinica, 2024, 40(10): 2312024-. doi: 10.3866/PKU.WHXB202312024
16. [16]
  Wenxiu Yang , Jinfeng Zhang , Quanlong Xu , Yun Yang , Lijie Zhang . Bimetallic AuCu Alloy Decorated Covalent Organic Frameworks for Efficient Photocatalytic Hydrogen Production. Acta Physico-Chimica Sinica, 2024, 40(10): 2312014-. doi: 10.3866/PKU.WHXB202312014
17. [17]
  Zhuo WANG , Junshan ZHANG , Shaoyan YANG , Lingyan ZHOU , Yedi LI , Yuanpei LAN . Preparation and photocatalytic performance of CeO₂-reduced graphene oxide by thermal decomposition. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1708-1718. doi: 10.11862/CJIC.20240067
18. [18]
  Wen YANG , Didi WANG , Ziyi HUANG , Yaping ZHOU , Yanyan FENG . La promoted hydrotalcite derived Ni-based catalysts: In situ preparation and CO₂ methanation performance. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 561-570. doi: 10.11862/CJIC.20230276
19. [19]
  Qiang ZHAO , Zhinan GUO , Shuying LI , Junli WANG , Zuopeng LI , Zhifang JIA , Kewei WANG , Yong GUO . Cu₂O/Bi₂MoO₆ Z-type heterojunction: Construction and photocatalytic degradation properties. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 885-894. doi: 10.11862/CJIC.20230435
20. [20]
  Wenjiang LI , Pingli GUAN , Rui YU , Yuansheng CHENG , Xianwen WEI . C₆₀-MoP-C nanoflowers van der Waals heterojunctions and its electrocatalytic hydrogen evolution performance. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 771-781. doi: 10.11862/CJIC.20230289

Get Citation

PDF

XML

Metrics

PDF Downloads(10)
Abstract views(803)
HTML views(92)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Total Synthesis of Dammarane-Type Saponins Ginsenoside Re and Notoginsenoside R1

Metrics

通讯作者: 陈斌, bchen63@163.com

Total Synthesis of Dammarane-Type Saponins Ginsenoside Re and Notoginsenoside R₁