补骨脂酚的化学与生物学研究进展
收稿日期: 2014-08-14
修回日期: 2014-09-09
网络出版日期: 2014-09-12
基金资助
上海市高校青年教师培养计划(No.yyy11015)和国家自然科学青年基金(No.21402121)资助项目
Chemistry and Biology of Bakuchiol
Received date: 2014-08-14
Revised date: 2014-09-09
Online published: 2014-09-12
Supported by
Project supported by the Young Teachers Program of Universities in Shanghai (No. yyy11015) and the National Natural Science Foundation of China (No. 21402121)
补骨脂是一种传统的中国及印度民间草药, 可用于治疗多种疾病. 补骨脂酚是从补骨脂中提取分离的一种重要单萜类化合物, 它具有广泛的药理活性, 是一个具有开发潜力的药物先导化合物. 开展新颖高效的补骨脂酚合成研究对进一步开发其药学用途具有重要理论意义和应用价值. 补骨脂酚全合成的关键在于其季碳中心的构建. 目前已有众多小组发展不同的策略来完成这项工作, 如醚类的Claisen重排反应; 乙烯基铜试剂对α,β-不饱和羰基化合物的1,4-加成反应; 环氧硅基醚的环氧重排反应; 分子内重氮磺酸盐对C—H的插入反应; 铜催化的SN2'型烯丙位取代反应; α,β-不饱和酰胺的α-烷基化反应以及烯丙基化反应. 介绍了近年来补骨脂酚的生理活性及其化学合成研究.
黄莎华 , 黄梦媛 , 贾学顺 , 洪然 . 补骨脂酚的化学与生物学研究进展[J]. 有机化学, 2014 , 34(12) : 2412 -2423 . DOI: 10.6023/cjoc201408015
Psoralea corylifolia (Linn.) has been used to treat a variety of diseases in both Chinese and Indian folkloric medicine. The moroterpene, bakuchiol, was isolated from the seeds of Psoralea corylifolia Linn. With a broad range of biological activities bakuchiol is considered as a leading compound for drug development. It is highly desirable to devise an efficient approach to access bakuchiol for further investigating its biologically relevant pathways. The key element in the total synthesis of bakuchiol relies on construction of the quaternary carbon stereocenter. This goal had been accomplished through several innovative strategies, such as Claisen rearrangement of geranyl enol ether, 1,4-addition of vinylcuprate species with α,β-unsaturated carbonyl compound, rearrangement of epoxy silyl ether, intramolecular diazosulfonate carbene insertion into a tertiary C—H bond, Cu-catalyzed SN2'-type allylic substitution, α-alkylation of α,β-unsaturated amide, allylmetalation, and allylboration. In this review, bioactivities and various synthetic routes of bakuchiol are discussed.
Key words： bakuchiol; bioactivity; total synthesis; quaternary carbon; review
[1] (a) Pharmacopoeia Commission of The People's Republic of China Pharmacopoeia of The People's Republic of China, China Medical Science Press, Beijing, 2010, p. 174 (in Chinese). (中华人民共和国药典委员会, 中华人民共和国药典, 中国医药科技出版社, 北京, 2010, p. 174.) (b) Editorial Committee of Flora Republicae Popularis Sinicae Flora Republicae Popularis Sinicae, Vol. 41, Eds.: Li, S.-G., Science Press, Beijing, 1995, pp. 344～346 (in Chinese). (中国植物志编委会, 中国植物志, 第41卷, 李树刚编著, 科学出版社, 北京, 1995, pp. 344～346.)
[2] (a) Labbe, C.; Faini, F.; Coll, J.; Connolly, J. D. Phytochemistry 1996, 42, 1299. (b) Wu, C. Z.; Cai, X. F.; Dat, N. T.; Hong, S. S.; Han, A. R.; Seo, E. K.; Hwang, B. Y.; Nan, J. X.; Lee, D.; Lee, J. J. Tetrahedron Lett. 2007, 48, 8861. (c) Wu, C. Z.; Hong, S. S.; Cai, X. F.; Dat, N. T.; Nan, J. X.; Hwang, B. Y.; Lee, J. J.; Lee, D. Bioorg. Med. Chem. Lett. 2008, 18, 2619. (d) Backhouse, C. N.; Delporte, C. L.; Negrete, R. E.; Cassels, B. K.; Schneider, C.; Breitmaier, E.; Feliciano, A. S. Phytochemistry 1995, 40, 325. (e) Yin, S.; Fan, C. Q.; Yue, J. M. J. Asian Nat. Prod. Res. 2007, 9, 29.
[3] Mehta, G.; Nayak, U. R.; Dev, S. Tetrahedron Lett. 1966, 7, 4561.
[4] Prakasar. A. S.; Bhalla, V. K.; Nayak, U. R.; Dev, S. Tetrahedron 1973, 29, 1127.
[5] Ji, L.; Xu, Z. L.; Yao, S. T. Chin. Pharm. J. 1995, 30, 436 (in Chinese). (吉力, 徐植灵, 姚三桃, 中国药学杂志, 1995, 30, 436.)
[6] Yan, D.-M.; Chang, Y.-X.; Kang, L.-Y.; Gao, X.-M. Chin. Herb. Med. 2010, 2, 216.
[7] Yao, S. T.; Yang, B.; Xu, Z. L. China J. Chin. Mater. Med. 1995, 20, 681 (in Chinese). (姚三桃, 杨滨, 徐植灵, 中国中药杂志, 1995, 20, 681.)
[8] Chen, Q. H.; Li, Y.; Chen, Z. L. J. Pharm. Anal. 2012, 2, 143.
[9] Liu, E. W.; Wang, J. L.; Han, L. F. J. Tianjin Univ. Trad. Chin. Med. 2012, 31, 95 (in Chinese). (刘二伟, 王家龙, 韩立峰, 天津中医药大学学报, 2012, 31, 95.)
[10] (a) Carnduff, J.; Miller, J. A. Chem. Commun. 1967, 606. (b) Carnduff, J.; Miller, J. A. J. Chem. Soc. (C) 1968, 2671.
[11] Yu, Y.; Wang, Y. J.; Pi, J. X.; Gao, X. J. Shangdong Univ. Tradit. Chin. Med. 2013, 37, 174 (in Chinese). (于悦, 王亚静, 皮佳鑫, 高旭, 山东中医药大学学报, 2013, 37, 174.)
[12] Antibacterial: (a) Katsura, H.; Tsukiyama, R.; Suzuki, A.; Kobayashi, M. Antimicrob. Agents Chemother. 2001, 45, 3009. (b) Reddy, M.; Thota, N.; Sangwan, P. L.; Malhotra, P.; Ali, F.; Khan, I. A.; Chimni, S. S.; Koul, S. Eur. J. Med. Chem. 2010, 45, 3125. (c) Newton, S. M.; Lau, C.; Gurcha, S. S.; Besra, G. S.; Wright, C. W. J. Ethnopharmacol. 2002, 79, 57. (d) Lau, K.-M.; Fu, L.-H.; Cheng, L.; Wong, C.-W.; Wong, Y.-L.; Lau, C.-P.; Han, S. Q.-B.; Chan, P. K.-S.; Fung, K.-P.; Lau, C. B.-S.; Hui, M.; Leung, P.-C. Am. J. Chin. Med. 2010, 45, 1005. (e) Madrid, A.; Espinoza, L.; González, C.; Mellado, M.; Villena, J.; Santander, R.; Silva, V.; Montenegro, I. J. Ethnopharmacol. 2012, 144, 809. (f) Guan, L. J.; Zhao, L. H.; Shao, S.; Li, S. Y. Chin. J. Biol. Cont. 2013, 29, 655. (in Chinese) (关丽杰, 赵礼慧, 邵双, 李海燕, 中国生物防治学报, 2013, 29, 655.)
[13] Antitumor: (a) Ryu, S.; Choi, S.; Lee, C.; Zee, O. Arch. Pharm. Res. 1992, 15, 356. (b) Chen, H. L.; Feng, H. J.; Li, Y. C. Acta Pharm. Sinica 2010, 45, 467 (in Chinese). (陈红莉, 冯慧瑾, 李援朝, 药学学报, 2010, 45, 467.)(c) Chen, Z. Ph.D. Dissertation, Zhejiang University, Hangzhou, 2010 (in Chinese). (陈哲, 博士论文, 浙江大学, 杭州, 2010.) d) Miao, L.; Ma, S. W.; Fan, G. W.; Wang, H.; Wang, Y. F.; Chai, L. J. Tianjin J. Tradit. Chin. Med. 2013, 30, 291 (in Chinese). (苗琳, 马尚伟, 樊官伟, 王虹, 王跃飞, 柴丽娟, 天津中医药, 2013, 30, 291.)
[14] Anti-inflammation: (a) Ferrandiz, M. L.; Gil, B.; Sanz, M. J.; Ubeda, A.; Erazo, S.; Gonzalez, E.; Negrete, R.; Pacheco, S.; Paya, M.; Alcaraz, M. J. J. Pharm. Pharmacol. 1996, 48, 975. (b) Matsuda, H.; Kiyohara, S.; Sugimoto, S.; Ando, S.; Nakamura, S.; Yoshikawa, M. Biol. Pharm. Bull. 2009, 32, 147. (c) Chai, L. J.; Wang, A. H.; Xu, J. H.; Wang, H.; Wang, S. X.; Zhang, H.; Zhang, X. X. Tradit. Chin. Drug Res. Pharmacol. 2013, 24, 360 (in Chinese). (柴丽娟, 王安红, 徐金虎, 王虹, 王少峡, 张晗, 张晓霞, 中药新药与临床药理, 2013, 24, 360.)
[15] Hypoglycemic activity: (a) Krenisky, J. M.; Luo, J.; Reed, M. J.; Carney, J. R. Biol. Pharm. Bull. 1999, 22, 1137. (b) Kim, Y.-C.; Oh, H.; Kim, B. S.; Kang, T.-H.; Ko, E.-K.; Han, Y. M.; Kim, B. Y.; Ahn, J. S. Planta Med. 2005, 71, 87.
[16] Antioxidant: (a) Cho, H.; Jun, J. Y.; Song, E. K.; Kang, K. H.; Baek, H. Y.; Ko, Y. S.; Kim, Y. C. Planta Med. 2001, 67, 750. (b) Haraguchi, H.; Inoue, J.; Tamura, Y.; Mizutani, K. Phytother. Res. 2002, 16, 539. (c) Park, E.-J.; Zhao, Y.-Z.; Kim, Y.-C.; Sohn, D. H. Planta Med. 2005, 71, 508. (d) Kim, K. A.; Shim, S. H.; Ahn, H. R.; Jung, S. H. Toxicol. Appl. Pharm. 2013, 269, 109.
[17] Phytoestrogenic activity: (a) Shou, Y. Q.; Yang, R. P.; Wang, B. H.; Liu, J. Y.; Xu, J. H. Tradit. Chin. Drug Res. Pharmacol. 2007, 11, 6 (in Chinese). (寿清耀, 杨荣平, 王宾豪, 刘剑毅, 徐嘉红, 中药新药与临床药理, 2007, 11, 6.)(b) Lim, S.-H.; Ha, T.-Y.; Kim, S.-R.; Ahn, J.; Park, H. J.; Kim, S. Br. J. Nutr. 2009, 101, 1031. (c) Xin, D.; Wang, H.; Yang, J.; Su, Y. F.; Fan, G. W.; Wang, Y. F.; Zhu, Y.; Gao, X. M. Phytomedicine 2010, 17, 126. (d) Mao, H. P.; Wang, H.; Ma, S. W.; Xu, Y. T.; Zhang, H.; Wang, Y. F.; Niu, Z. C.; Fan, G. W.; Zhu, Y.; Gao, X. M. Toxicol. Appl. Pharm. 2014, 274, 180.
[18] Depigmenting effect: Ohno, O.; Watabe, T.; Nakamura, K.; Kawagoshi, M.; Uotsu, N.; Chiba, T.; Yamada, M.; Yamaguchi, K.; Yamada, K.; Miyamoto, K.; Uemura, D. Biosci. Biotechnol. Biochem. 2010, 74, 1504.
[19] Cytotoxicity: (a) Zhang, Y. S.; Liu, Y. Q.; Wu, Z. L.; Wang, Y. P. China J. Chin. Mater. Med. 1981, 6, 30 (in Chinese). (张玉顺, 刘玉琦, 吴子伦, 王雁平, 中国中药杂志, 1981, 6, 30.)(b) Sun, N. J.; Woo, S. H.; Cassady, J. M.; Snapka, R. M. J. Nat. Prod. 1998, 61, 362; (c) Jiang, F.; Zhou, X. R.; Wang, Q.; Zhang, B. X. Chin. J. Pharmacol. Toxicol. 2010, 24, 50 (in Chinese). (江芳, 周昕睿, 王旗, 张宝旭, 中国药理学与毒理学杂志, 2010, 24, 50.)(d) Jiao, S. Y.; Ai, C. H.; Li, A. F.; Li, H.; Wang, Q. Chin. Pharm. Bull. 2011, 27, 216 (in Chinese). (焦士勇, 艾常虹, 李艾芳, 李桦, 王旗, 中国药理学通报, 2011, 27, 216.)(e) Li, A. F.; Shen, G. L.; Jiao, S. Y.; Li, H.; Wang, Q. J. Peking Univ. (Health Sci.) 2012, 44, 431 (in Chinese). (李艾芳, 沈国林, 焦士勇, 李桦, 王旗, 北京大学学报, 2012, 44, 431.)
[20] (a) Zhuang, X. M.; Zhong, Y. H.; Yuan, M.; Li, H. J. Pharm. Biomed. 2013, 75, 18. (b) Gao, X.; Wang, Y. J.; Pi, J. X.; Zheng, Y.; Yu, Y.; Xuan, X. Y. Chin. Tradit. Pat. Med. 2013, 35, 2122 (in Chinese). (高旭, 王亚静, 皮佳鑫, 郑银, 于悦, 轩肖玉, 中成药, 2013, 35, 2122.)
[21] (a) Damodara, N. P.; Dev, S. Tetrahedron Lett. 1967, 8, 2897. (b) Shi, L.; Lei, X. S.; Zhang, J.; Lin, G. Q. Helv. Chim. Acta 2010, 93, 555. (c) Takao, K.; Sakamoto, S.; Touati, M. A.; Kusakawa, Y.; Tadano, K. Molecules 2012, 17, 13330.
[22] (a) Takano, S.; Shimazaki, Y.; Ogasawara, K. Tetrahedron Lett. 1990, 31, 3325. (b) Esumi, T.; Shimizu, H.; Kashiyama, A.; Sasaki, C.; Toyota, M.; Fukuyama, Y. Tetrahedron Lett. 2008, 49, 6846. (c) Esumi, T.; Yamamoto, C.; Sasaki, C.; Toyota, M.; Fukuyama, Y. Synlett 2013, 24, 1845. (d) Chen, H. L.; Li, Y. C. Lett. Org. Chem. 2008, 5, 467.
[23] Du, X. L.; Chen, H. L.; Feng, H. J.; Li, Y. C. Helv. Chim. Acta 2008, 91, 371.
[24] Bequette, J. P.; Jungong, C. S.; Novikov, A. V. Tetrahedron Lett. 2009, 50, 6963.
[25] Gao, F.; McGrath, K. P.; Lee, Y.; Hoveyda, A. H. J. Am. Chem. Soc. 2010, 132, 14315.
[26] (a) Sakakiyama, S.; Yamamoto, K.; Asaoka, M. Nat. Prod. Lett. 1999, 14, 1. (b) Asaoka, M.; Takenouchi, K.; Takei, H. Tetrahedron Lett. 1988, 29, 325. (c) Xu, Q. Q.; Zhao, Q.; Shan, G. S.; Yang, X. C.; Shi, Q. Y.; Lei, X.- S. Tetrahedron 2013, 69, 10739. (d) Zhao, Q.; Xu, Q.; Shan, G.; Dong, C.; Zhang, H.; Lei, X. S. Molecules 2014, 19, 2213.
[27] (a) Araki, S.; Bustugan, Y. J. Chem. Soc., Perkin Trans. 1 1991, 2395. (b) Huang, M.-Y.; Chen, L.; Li, R.; Jia, X.; Hong, R. Chin. J. Chem. 2014, 32, 715.
[28] Huo, H.-X.; Huang, M.-Y.; Duvall, J. R.; Hong, R. Org. Chem. Front. 2014, 1, 303.
/
| 〈 |
|
〉 |
