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

doi:10.6023/cjoc202403006

Chinese Journal of Organic Chemistry ›› 2024, Vol. 44 ›› Issue (9): 2862-2868.DOI: 10.6023/cjoc202403006 Previous Articles Next Articles

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防风中亥茅酚及亥茅酚苷的不对称合成

曾涛, 张曙盛, 付建国^*(), 冯陈国^*()

上海中医药大学创新中药研究院上海 201203

收稿日期:2024-03-04 修回日期:2024-04-15 发布日期:2024-05-16
通讯作者: 付建国, 冯陈国
基金资助:
国家自然科学基金(22271195); 国家自然科学基金(22301185); 上海市科学技术委员会(21ZR1482100); 上海市科学技术委员会(22ZR1458900); 上海市中央引导地方科技发展资金(YDZX20223100001004); 上海中医药大学有组织科研计划(2023YZZ01); 及上海中医药大学预算内(2021LK001)

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

Tao Zeng, Shusheng Zhang, Jianguo Fu(), Chenguo Feng()

Innovation Research Institute of Traditional Chinese Medicine, Shanghai University of Traditional Chinese Medicine, Shanghai 201203

Received:2024-03-04 Revised:2024-04-15 Published:2024-05-16
Contact: Jianguo Fu, Chenguo Feng
Supported by:
National Natural Science Foundation of China(22271195); National Natural Science Foundation of China(22301185); Science and Technology Commission of Shanghai Municipality(21ZR1482100); Science and Technology Commission of Shanghai Municipality(22ZR1458900); Shanghai Science and Technology Development Fund from Central Leading Local Government(YDZX20223100001004); Organizational Key R&D Program of Shanghai University of Traditional Chinese Medicine(2023YZZ01); Expenditure Budget Program of Shanghai University of Traditional Chinese Medicine(2021LK001)

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Abstract

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.

Key words: Saposhnikovia Divaricata (Turcz.) schischk, chromone, hamaudol, sec-O-glucosylhamaudol, asymmetric synthesis

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Tao Zeng, Shusheng Zhang, Jianguo Fu, Chenguo Feng. Asymmetric Synthesis of Hamaudol and sec-O-Glucosylhamaudol in Saposhnikovia divaricata (Turcz.) Schischk[J]. Chinese Journal of Organic Chemistry, 2024, 44(9): 2862-2868.

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References 24

[1]	Cao, S.-S.; Shi, L.; Sun, J.-L.; Meng, X.-C. Res. Pract. Chin. Med. 2021, 35, 95 (in Chinese).
	(曹思思, 史磊, 孙佳琳, 孟祥才, 现代中药研究与实践, 2021, 35, 95.)
[2]	Yang, M.; Wang, C.-C.; Wang, W.-L. Chin. J. Integr. Med. 2020, 26, 873.
[3]	Li, L.; Gui, Y.-G.; Shi, D.-F.; Liu, C.-M. Lishizhen Med. Mater. Med. Res. 2010, 21, 2135 (in Chinese).
	(李丽, 桂语歌, 时东方, 刘春明, 时珍国医国药, 2010, 21, 2135.)
[4]	Han, B.; Dai, Y.; Wu, H. Med. Sci. Monit. 2019, 25, 409.
[5]	Wei, L.-B.; Ma, S.-Y.; Gu, Z.-B.; Wei, Q.-Q. Chem. Nat. Prod. 2022, 58, 230
[6]	(a) Cao, J.; Zhou, M.-X.; Chen, X. Front Immunol. 2022, 13, 880988.
	(b) Duan, J.; Hu, X.; Li, T. Front. Pharmacol. 2021, 12.
[7]	(a) Liu, G.; Xie, J.; Shi, Y.; Chen, R.; Li, L.; Wang, M.; Zheng, M.; Xu, J. Biosci. Rep. 2020, 40, BSR20194230.
	(b) Li, Y.-L.; Xue, X.; Han, T.; Li, X.-R. Mod. Chin. Med. 2021, 23, 1195 (in Chinese).
	(李依林, 薛雪, 韩婷, 李向日, 中国现代中药, 2021, 23, 1195.)
[8]	Wang, H.; Guo, L.-G.; Shang, X.-P. Chin. Tradit. Herb. Drugs 2020, 51, 5320 (in Chinese).
	(王浩, 郭凌阁, 尚兴朴, 中草药, 2020, 51, 5320.)
[9]	(a) Tang, D.; Wang, C.; Gu, Z.; Li, J.; Jin, L.; Li, J.; Wang, Z.; Jiang, R. W. Phytomedicine 2023, 115, 154837.
	(b) Zheng, M. S.; Son, K. H.; Chang, H. W.; Kim, H. P.; Kang, S. S.; Jin, W. Y. Korean J. Med. Crop Sci. 2005, 13, 75.
[10]	Lal, B.; Kansal, VK.; Singh, R. Indian J. Chem.,Sect. B: Org. Chem. Incl. Med. Chem. 1998, 37, 881.
[11]	Yasushi, I. JP 2015168625, 2015
[12]	Wu, J.; Mu, R.; Sun, M. ACS Infect. Dis. 2019, 5, 1087.
[13]	Madabhushi, S.; Jillella, R.; Godala, K. R. Tetrahedron Lett. 2012, 53, 5275
[14]	Evans, J. M.; Fake, C. S.; Hamilton, T. C. J. Med. Chem. 1983, 26, 1582 pmid: 6631915
[15]	North, J. T.; Kronenthal, D. R.; Pullockaran, A. J. J. Org. Chem. 1995, 60, 3397.
[16]	Saimoto, H.; Yoshida, K.; Murakami, T.; Morimoto, M.; Sashiwa, H.; Shigemasa, Y. J. Org. Chem. 1996, 61, 6768.
[17]	(a) Mondal, M.; Puranik, V. G.; Argade, N. P. J. Org. Chem. 2006, 71, 4992.
	(b) Yen, C.-T.; Nakagawa-Goto, K.; Hwang, T.-L. Bioorg. Med. Chem. Lett. 2012, 22, 4018.
	(c) Selepe, M. A.; Drewes, S. E.; van Heerden, F. R. J. Nat. Prod. 2010, 73, 1680.
	(d) Kim, E.-S.; Kim, H. J. Nat. Prod. 2018, 81, 2647
[18]	(a) Zhang, W.; Loebach, J. L.; Wilson, S. R.; Jacobsen, E. N. J. Am. Chem. Soc. 1990, 112, 2801.
	(b) Jacobsen, E. N. Acc. Chem. Res. 2000, 33, 421.
[19]	(a) Lim, J.; Kim, I.-H.; Kim, H.-H. Tetrahedron Lett. 2001, 42, 4001.
	(b) Bujons, J.; Camps, F.; Messeguer, A. Tetrahedron Lett. 1990, 31, 5235.
[20]	(a) Katsuki, T.; Sharpless, K. B. J. Am. Chem. Soc. 1980, 102, 5974.
	(b) Engle, K. M.; Mei, T.-S.; Wasa, M.; Yu, J.-Q. Acc. Chem. Res. 2012, 45, 788.
[21]	(a) Tu, Y.; Wang, Z.-X.; Shi, Y. J. Am. Chem. Soc. 1996, 118, 9806.
	(b) Li, A. H.; Dai, L. X.; Aggarwal, V. K. Chem. Rev. 1997, 97, 2341.
[22]	Sasaki, H.; Taguchi, H.; Endo, T.; Yosioka, I. Chem. Pharm. Bull. 1982, 30, 3555.
[23]	Bruder, M.; Haseler, PL.; Muscarella, M. J. Org. Chem. 2010, 75, 353.
[24]	Jain, AC.; Gupta, A.; Kumari, S. Indian J. Chem.,Sect. B: Org. Chem. Incl. Med. Chem. 1983, 22B, 365.

Entry	Conditions	Yield/%	Ratio of 4/10
1	BF₃•Et₂O, DCM, r.t.	N.R.^a	—
2	K₂CO₃, acetone, reflux	N.R.^a	—
3	3-picoline, p-xylene, 115 ℃	10	0.6∶1
4	EDDA,^b toluene, 115 ℃	16	0.4∶1
5	Ca(OH)₂, MeOH, r.t.	51	17∶1

Entry	Conditions	Yield/%	Ratio of 4/10
1	BF₃•Et₂O, DCM, r.t.	N.R.^a	—
2	K₂CO₃, acetone, reflux	N.R.^a	—
3	3-picoline, p-xylene, 115 ℃	10	0.6∶1
4	EDDA,^b toluene, 115 ℃	16	0.4∶1
5	Ca(OH)₂, MeOH, r.t.	51	17∶1

Entry	R	Catalyst & oxidant	Temp./℃	Solvent	Yield/%	ee/%
1	H	Jacobsen's Cat. (S,S) & Oxone	0	MeCN/buffer	N.D.^a	—
2	Ac	Jacobsen's Cat. (S,S) & Oxone	0	MeCN/buffer^b	81	65
3	Ac	Jacobsen's Cat. (S,S) & Oxone	－10	MeCN/buffer^c	85	91
4	Me	Jacobsen's Cat. (S,S) & Oxone	－10	MeCN/buffer^c	80	87
5	Ac	L-(＋)-DET/Ti(Oi-Pr) & t-BuOOH	－48	DCM	N.R.^b	—
6	Ac	Shi's Cat. & Oxone	－10	MeCN/buffer^c	Trace	—

Entry	R	Catalyst & oxidant	Temp./℃	Solvent	Yield/%	ee/%
1	H	Jacobsen's Cat. (S,S) & Oxone	0	MeCN/buffer	N.D.^a	—
2	Ac	Jacobsen's Cat. (S,S) & Oxone	0	MeCN/buffer^b	81	65
3	Ac	Jacobsen's Cat. (S,S) & Oxone	－10	MeCN/buffer^c	85	91
4	Me	Jacobsen's Cat. (S,S) & Oxone	－10	MeCN/buffer^c	80	87
5	Ac	L-(＋)-DET/Ti(Oi-Pr) & t-BuOOH	－48	DCM	N.R.^b	—
6	Ac	Shi's Cat. & Oxone	－10	MeCN/buffer^c	Trace	—

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

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