Total Synthesis of (±)-Hongoquercin A via Visible-Light-Mediated Organocatalytic Polyene Cyclization

doi:10.6023/A16110591

Acta Chim. Sinica ›› 2017, Vol. 75 ›› Issue (4): 351-354.DOI: 10.6023/A16110591 Previous Articles Next Articles

Communication

(±)-Hongoquercin A全合成:可见光促进有机催化多烯环化策略

杨忠波, 李速家, 罗三中

中国科学院化学研究所分子识别与功能院重点实验室北京 100190

投稿日期:2016-11-08 发布日期:2017-03-21
通讯作者: 罗三中,E-mail:luosz@iccas.ac.cn;Tel.:0086-010-62554446 E-mail:luosz@iccas.ac.cn
基金资助:
项目受科技部（No.2012CB821600）和国家自然科学基金（Nos.21390400，21521002）资助.罗三中感谢中组部拔尖人才计划的支持.

Total Synthesis of (±)-Hongoquercin A via Visible-Light-Mediated Organocatalytic Polyene Cyclization

Yang Zhongbo, Li Sujia, Luo Sanzhong

Key Laboratory of Molecular Recognition and Functions, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190

Received:2016-11-08 Published:2017-03-21
Contact: 10.6023/A16110591 E-mail:luosz@iccas.ac.cn
Supported by:
Project supported by the Ministry of Science and Technology (No. 2012CB821600) and the Natural Science Foundation of China (Nos. 21390400, 21521002).

1. Total Synthesis of (±)-Hongoquercin A via Visible-Light-Mediated Organocatalytic Polyene Cyclization.PDF(405KB)

Abstract

Advances in the strategy and methodology of visible light photocatalysis have begun to alter the way how organic chemists address the synthetic problems. These powerful methods have enabled the development of novel reaction schemes and approaches (mostly via radical path) for the total synthesis of nature products under visible light photoredox catalysis. Terpenoids, possessing intriguing biological activities together with their structural diversity, have remained as attractive targets for chemists. On the basis of their biogenetic pathways, polyene cyclization is the most straightforward pathway to attain terpenoid skeletons. Most recently, a few examples of stereoselective radical polyene cyclizations have been developed. However, most of the radical approaches suffer from the requirement for stoichiometric loading of metals or radical initiators. And in many cases, low yields are obtained with complicated reaction mixtures, which cumber further development along this line especially in nature products synthesis. In our previous work, we have developed a visible-light-mediated, stereoselective organocatalytic cyclization of polyenes. The wide scope as well as the high chemoselectivity inspires us to apply this method in the total synthesis of terpenoid natural products. Thus we report here total synthesis of (±)-Hongoquercin A (1), starting from trans,trans-farnesol (4) in 7 steps and with overall 14.4% yield. Our developed visible-light-mediated redox organocatalytic methodology is employed as the key step to construct multiple ring-fused skeleton of 1 in one step.[To a flame-dried Schlenk tube equipped with a magnetic stir bar was added 3-hydroxy-5-methyl-2-((2E,6E)-3,7,11-trimethyl-dodeca-2,6,10-trien-1-yl)cyclohex-2-enone (3) (0.20 g, 0.61 mmol) and Eosin Y (4.0 mg, 0.0061 mmol). The mixture was diluted with 1.5 mL of anhydrous hexafluoroisopropanol. The reaction was irradiated with Green LEDs at room temperature for 2 h. Upon completion, the reaction mixture was concentrated in vacuo. The residue was purified by silica gel chromatography (10% EtOAc in Petroleum ether) to give 2 (ca. 60% yield, colorless oil) containing all the skeleton carbons of Hongoquercin A.

Key words: total synthesis, terpenoid, Hongoquercin A, visible-light-driven, cation radical polyene cyclization

Cite this article

Yang Zhongbo, Li Sujia, Luo Sanzhong. Total Synthesis of (±)-Hongoquercin A via Visible-Light-Mediated Organocatalytic Polyene Cyclization[J]. Acta Chim. Sinica, 2017, 75(4): 351-354.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

References

[1] (a) Nicolaou, K. C.; Vourloumis, D.; Wissinger, N.; Baran, P. S. Angew. Chem. Int. Ed. 2000, 39, 44.
(b) Nicolaou, K. C.; Montagnon, T.; Snyder, S. A. Chem. Commun. 2003, 551.
(c) Nicolaou, K. C.; Edmonds, D. J.; Bulger, P. G. Angew. Chem. Int. Ed. 2006, 45, 7134.
(d) Maimone, T. J.; Baran, P. S. Nat. Chem. Biol. 2007, 3, 396.
[2] For a recent review, see:(a) Yoder, R. A.; Johnston, J. N. Chem. Rev. 2005, 105, 4730; For early contributions, see:
(b) Johnson, W. S.; Kinnel, R. B. J. Am. Chem. Soc. 1966, 88, 3861.
(c) Tamelen, E. E. V.; McCormick, J. P. J. Am. Chem. Soc. 1969, 91, 1847.
[3] For selected examples in this field, see:(a) Ishihara, K.; Nakamura, S.; Yamamoto, H. J. Am. Chem. Soc. 1999, 121, 4906.
(b) Ishihara, K.; Ishibashi, H.; Yamamoto, H. J. Am. Chem. Soc. 2001, 123, 1505.
(c) Ishibashi, H.; Ishihara, K.; Yamamoto, H. J. Am. Chem. Soc. 2004, 126, 11122.
(d) Surendra, K.; Corey, E. J. J. Am. Chem. Soc. 2012, 134, 11992.
(e) Zhao, Y.-J.; Li, B.; Tan, L.-J. S.; Shen, Z.-L.; Loh, T.-P. J. Am. Chem. Soc. 2010, 132, 10242.
(f) Sakakura, A.; Ukai, A.; Ishihara, K. Nature 2007, 445, 900.
(g) Rendler, S.; MacMillan, D. W. C. J. Am. Chem. Soc. 2010, 132, 5027.
(h) Knowles, R. R.; Lin, S.; Jacobsen, E. N. J. Am. Chem. Soc. 2010, 132, 5030.
(i) Mullen, C. A.; Campbell, A. N.; Gagn, M. R. Angew. Chem. Int. Ed. 2008, 47, 6011.
(j) Sethofer, S. G.; Mayer, T.; Toste, F. D. J. Am. Chem. Soc. 2010, 132, 8276.
(k) Schafroth, M. A.; Sarlah, D.; Krautwald, S.; Carreira, E. M. J. Am. Chem. Soc. 2012, 134, 20276.
[4] For a recent review, see:(a) Justicia, J.; Álvarez de Cienfuegos, L.; Campaña, A. G.; Miguel, D.; Jakoby, V.; Gansäuer, A.; Cuerva, J. M. Chem. Soc. Rev. 2011, 40, 3525. For selected examples, see:
(b) Rendeler, S.; MacMillan, D. W. C. J. Am. Chem. Soc. 2010, 132, 5027.
(c) Handa, S.; Pattenden, G. J. Chem. Soc., Perkin Trans. 11999, 843.
(d) Kates, S. A.; Dombroski, M. A.; Snider, B. B. J. Org. Chem. 1990, 55, 2427.
(e) Zoretic, P. A.; Fang, H.; Ribeiro, A. A. J. Org. Chem. 1998, 63, 4779.
(f) Morcillo, S. P.; Miguel, D.; Resa, S.; Martín-Lasanta, A.; Millán, A.; Choquesillo-Lazarte, D.; Gar-cía-Ruiz, J. M.; Mota, A. J.; Justicia, J.; Cuerva, J. M. J. Am. Chem. Soc. 2014, 136, 6943.
(g) Gu, S.; Yan, Y.-L.; Zhao, H.-W.; Zhu, N.-Y.; Yang, D. Angew. Chem. Int. Ed. 2002, 41, 3014.
(h) Heinemann, C.; Demuth, M. J. Am. Chem. Soc. 1999, 121, 4894.
(i) Bunte, J. O.; Rinne, S.; Schäfer, C.; Neumann, B.; Stammlerb, H.-G.; Mattaya, J. Tetrahedron Lett. 2003, 44, 45.
[5] For recent selected reviews on the field of photocatalysis in photochemical synthesis, see:(a) Skubi, K. L.; Blum, T. R.; Yoon, T. P. Chem. Rev. 2016, 116, 10035.
(b) Romero, N. A.; Nicewicz, D. A. Chem. Rev. 2016, 116, 10075.
(c) Corrigan, N.; Shanmugam, S.; Xu, J.; Boyer, C. Chem. Soc. Rev. 2016, 45, 6165.
(d) Shaw, M. H.; Twilton, J.; MacMillan, D. W. C. J. Org. Chem. 2016, 81, 6898. For reviews on the field of visible-light photoredox catalysis, see:
(e) Ding, K.; Xiao, W.; Wu, L.-Z. Acta Chim. Sinica 2017, 75, 5(in Chinese). (丁奎岭, 肖文精, 吴骊珠, 化学学报, 2017, 75, 5.)
(f) Pei, P. Zhang, F.; Yi, H.; Lei, A. Acta Chim. Sinica 2017, 75, 15(in Chinese). (裴朋昆, 张凡, 易红, 雷爱文, 化学学报, 2017, 75, 15.)
(g) Wang, D.; Zhang, L.; Luo, S. Acta Chim. Sinica 2017, 75, 22(in Chinese). (王德红, 张龙, 罗三中, 化学学报, 2017, 75, 22.)
(h) Zhong, J.-J.; Meng, Q.-Y.; Chen, B.; Tung, C.-H.; Wu, L.-Z. Acta Chim. Sinica 2017, 75, 34(in Chinese). (钟建基, 孟庆元, 陈彬, 佟振合, 吴骊珠, 化学学报, 2017, 75, 34.)
(i) Zhang, J.; Chen, Y. Acta Chim. Sinica 2017, 75, 41(in Chinese). (张晶, 陈以昀, 化学学报, 2017, 75, 41.)
(j) Guan, B.; Xu, X.; Wang, H.; Li, X. Chin. J. Org. Chem. 2016, 36, 1564(in Chinese). (关保川, 许孝良, 王红, 李小年, 有机化学, 2016, 36, 1564.)
(k) Sun, X.; Yu, S. Chin. J. Org. Chem. 2016, 36, 239(in Chinese). (孙晓阳, 俞寿云, 有机化学, 2016, 36, 239.)
(l) Schultz, D. M.; Yoon, T. P. Science 2014, 343, 1239176.
(m) Prier, C. K.; Rankic, D. A.; MacMillan, D. W. C. Chem. Rev. 2013, 113, 5322.
(n) Xuan, J.; Lu, L.-Q.; Chen, J.-R.; Xiao, W.-J. Eur. J. Org. Chem. 2013, 6755.
(o) Narayanam, J. M. R.; Stephenson, C. R. J. Chem. Soc. Rev. 2011, 40, 102.
(p) Zeitler, K. Angew. Chem. Int. Ed. 2009, 48, 9785.
[6] For recently selected reviews on the field of applications of visible light photoredox catalysis in natural product synthesis, see:(a) Nicholls, T. P.; Leonori, D.; Bissember, A. C. Nat. Prod. Rep. 2016, 33, 1248.
(b) Kärkäs, M. D.; Porco, J. A., Jr.; Stephenson, C. R. J. Chem. Rev. 2016, 116, 9683.
(c) Tan, F.; Xiao, W. Acta Chim. Sinica 2015, 73, 85(in Chinese). (谭芬, 肖文精, 化学学报, 2015, 73, 85.)
[7] Yang, Z.; Li, H.; Zhang, L.; Zhang, M.-T.; Cheng, J.-P.; Luo, S. Chem. Eur. J. 2015, 21, 14723.
[8] (a) Roll, D. M.; Manning, J. K.; Carter, G. T. J. Antibiot. 1998, 51, 635. For fermentation studies, see:
(b) Abbanat, D. A.; Singh, M. P.; Greenstein, M. J. Antibiot. 1998, 51, 708.
[9] Tsujimori, H.; Bando, M.; Mori, K. Eur. J. Org. Chem. 2000, 297.
[10] Kurdyumov, A. V.; Hsung, R. P. J. Am. Chem. Soc. 2006, 128, 6272.
[11] Rosen, B. R.; Simke, L. R.; Thuy-Boun, P. S.; Dixon, D. D.; Yu, J.-Q.; Baran, P. S. Angew. Chem. Int. Ed. 2013, 52, 7317.
[12] For reviews on the field of photochemical reactions as key steps in natural product synthesis, see:(a) Bach, T.; Hehn. J. P. Angew. Chem. Int. Ed. 2011, 50, 1000.
(b) Hoffmann. N. Chem. Rev. 2008, 108, 1052.
(c) Iriondo-Alberdi, J.; Greaney, M. F. Eur. J. Org. Chem. 2007, 4801.
[13] For recently selected examples on the field of applications of DDQ as aromatization reagent in natural product synthesis, see:(a) Li, H.; Chen, Q.; Lu, Z.; Li, A. J. Am. Chem. Soc. 2016, 138, 15555.
(b) Yang, P.; Yao, M.; Li, J.; Li, Y.; Li, A. Angew. Chem. Int. Ed. 2016, 55, 6964.
(c) Zhou, S.; Chen, H.; Luo, Y.; Zhang, W.; Li, A. Angew. Chem. Int. Ed. 2015, 54, 6878.

[1]	Jie Zhao, Zhiwen Wang, Huaqing Li, Qi Ai, Peiqing Cai, Junjie Si, Xin Yao, Xiaoguang Hu, Zugang Liu. Synthesis and Properties of Visible-light-driven Fluorescence Turn-on Diarylethenes Based on Benzo[b]naphtho[1,2-d]thiophene [J]. Acta Chimica Sinica, 2022, 80(9): 1223-1230.
[2]	Yang Baochao, Gao Shuanhu. Application of Photochemical Rearrangement of Santonin in Total Synthesis of Complex Natural Terpenoids [J]. Acta Chim. Sinica, 2018, 76(3): 161-167.
[3]	Yu Kuan, Gao Beiling, Ding Hanfeng. Asymmetric Total Synthesis and Absolute Configuration Reassignment of Indole Alkaloid (+)-Alsmaphorazine D [J]. Acta Chim. Sinica, 2016, 74(5): 410-414.
[4]	Liu Rong, Feng Jing, Liu Bo. Synthetic Progress of Daphnane-type Diterpenoids [J]. Acta Chim. Sinica, 2016, 74(1): 24-43.
[5]	Tan Fen, Xiao Wenjing. Visible-Light Photoredox Catalysis in Natural Products Synthesis [J]. Acta Chim. Sinica, 2015, 73(2): 85-89.
[6]	Li Sena, Han Jing, Li Ang. Interrupted Fisher Indole Synthesis and Its Applications to Alkaloid Synthesis [J]. Acta Chimica Sinica, 2013, 71(03): 295-298.
[7]	Zhang Dan, Qin Yong. Oxidative Coupling Strategy in the Total Syntheses of Complex Indole Alkaloids [J]. Acta Chimica Sinica, 2013, 71(02): 147-150.
[8]	Yue Xiaodong, Chen Li, Li Weidong. Reactivities of Substituted Azulenone: Strategic Exploration on the Novel Synthesis of Colchicine [J]. Acta Chimica Sinica, 2012, 70(19): 2029-2036.
[9]	YUAN Hu, HAN Wei, YANG Wei-Zhun, DAN Lei, ZHANG Wei-Dong, SUN Qing-Yan. Total Synthesis of Natural Product (＋)-2-(1-Hydroxyl-4-oxocyclohexyl)ethyl Caffeate as a Modulator of Leukotriene A4 Hydrolase [J]. Acta Chimica Sinica, 2011, 69(22): 2691-2695.
[10]	HAN Tian-Jiao, SONG Feng-Rui, LIU Zhong-Ying, PI Zi-Feng, LIU Zhi-Qiang, LIU Shu-Ying. Studies of the Intestinal Transport of the Diterpenoid Alkaloids in the Aconitum carmichaeli Combined with Different Medicinal Herbs in a Caco-2 Cell Culture System with UPLC/MS [J]. Acta Chimica Sinica, 2011, 69(15): 1795-1802.
[11]	YUAN Hu, DAN Lei, SUN Qing-Yan, HAN Wei. Total Synthesis of (±)-Rosmarinic Acid [J]. Acta Chimica Sinica, 2011, 69(08): 945-948.
[12]	TANG Hui-Yang, HAN Yu-Mei, YAN Dan, ZHANG Shao-Feng, LUO Yun, XIAO Xiao-He, LIU Rong-Hua, BANG Cheng. Microcalorimetric Investigation of Toxic Effects of Diester Diterpenoid Alkaloids from Aconiti Class on Tetrahymena thermophila BF5 Growth [J]. Acta Chimica Sinica, 2010, 68(03): 205-210.
[13]	. Chemical Constitutes of Garcinia hanburyi [J]. Acta Chimica Sinica, 2008, 66(22): 2513-2517.
[14]	. An Expeditious Synthesis of (±)-Bruguierol A [J]. Acta Chimica Sinica, 2008, 66(19): 2138-2140.
[15]	OUYANG, Jie; QIAO, Kun; ZHANG, Wei; DENG, Zhi-Wei*^,1; LI, Li-Ya²; LIN, Wen-Han². NMR Structural Elucidation of 3,4-Seco-olean-11,13-dien- 4,15α,22β,24-tetraol-3-oic Acid with Modulation of Water Peak [J]. Acta Chimica Sinica, 2008, 66(11): 1327-1332.

(±)-Hongoquercin A全合成:可见光促进有机催化多烯环化策略

Total Synthesis of (±)-Hongoquercin A via Visible-Light-Mediated Organocatalytic Polyene Cyclization

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments