Citation: Zheng Xiuwen, Ma Haiyan, Ding Kai. Practical Syntheses of Equilin and Its Derivatives[J]. Chinese Journal of Organic Chemistry, ;2018, 38(2): 464-470. doi: 10.6023/cjoc201709005 shu

Practical Syntheses of Equilin and Its Derivatives

Zheng Xiuwen ^a,b ,
Ma Haiyan ^a,, ,
Ding Kai ^b,,

a.
Laboratory of Organometallic Chemistry, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237
b.
CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Corresponding author: Ma Haiyan, haiyanma@ecust.edu.cn Ding Kai, dingkai@mail.sioc.ac.cn
Received Date: 5 September 2017
Revised Date: 11 October 2017
Available Online: 16 February 2017

Figures(5)

Equilin and its derivatives are important active ingredients of conjugated estrogens, extracted from pregnant horse urine. However, they are still challenge synthetic targets due to the presence of an unstable non-conjugated double bond. Equilin (7), 17β-dihydroequilin (8) and 17α-dihydroequilin (9) were efficiently synthesized from commercially available 19-hydroxyandrost-4-ene-3, 17-dione via retro-aldol aromatization with the overall yields of 32%, 37% and 25%, respectively.
- equilin,
- conjugated estrogen,
- aromatization,
- steroid
1. [1]
  (a) Grodin, J. M. ; Siiteri, P. K. ; Macdonald, P. C. J. Clin. Endocrinol. Metab. 1973, 36, 207.
  (b) Longcope, C. Am. J. Obstet. Gynecol. 1971, 111, 778.
  (c) Purohit, A. ; Tutill, H. J. ; Day, J. M. ; Chander, S. K. ; Lawrence, H. R. ; Allan, G. M. ; Fischer, D. S. ; Vicker, N. ; Newman, S. P. ; Potter, B. V. L. ; Reed, M. J. Mol. Cell. Endocrinol. 2006, 248, 199.
2. [2]
  Bhavnani, B. R.; Stanczyk, F. Z. J. Steroid Biochem. Mol. Biol. 2014, 142, 16. doi: 10.1016/j.jsbmb.2013.10.011
3. [3]
4. [4]
  Yue, T.; Li, H. -P.; Ding, K. Tetrahedron Lett. 2016, 57, 4850. doi: 10.1016/j.tetlet.2016.09.062
5. [5]
  (a) Zderic, J. A. ; Bowers, A. ; Carpio, H. ; Djerassi, C. J. Am. Chem. Soc. 1958, 80, 2596.
  (b) Zderic, J. A. ; Carpio, H. ; Bowers, A. ; Djerassi, C. Steroids 1963, 1, 233.
  (c) Bagli, J. F. ; Morand, P. F. ; Wiesner, K. ; Gaudry, R. Tetrahedron Lett. 1964, 5, 387.
  (d) Stein, R. P. ; Buzby, G. C. ; Smith, H. Tetrahedron Lett. 1966, (41), 5015.
  (e) Stein, R. P. ; Buzby, G. C. ; Smith, H. Tetrahedron 1970, 26, 1917.
  (f) Bailey, E. J. ; Gale, A. ; Phillipp, G. ; Siddons, P. T. ; Smith, G., Chem. Commun. 1967, 1253.
  (g) Marshall, D. J. ; Deghengh, R. Can. J. Chem. 1969, 47, 3127.
6. [6]
  Zheng, D. -Q.; Jing, Y.; Zheng, B. -Y.; Ye, Y. -F.; Xu, S.; Tian, W. -S.; Ma, H. -Y.; Ding, K. Tetrahedron 2016, 72, 2164. doi: 10.1016/j.tet.2016.03.002
7. [7]
  (a) Nicolaou, K. C. ; Zhong, Y. L. ; Baran, P. S. J. Am. Chem. Soc. 2000, 122, 7596.
  (b) Nicolaou, K. C. ; Montagnon, T. ; Baran, P. S. ; Zhong, Y. L. J. Am. Chem. Soc. 2002, 124, 2245.
  (c) Chen, K. ; Liu, C. ; Deng, L. ; Xu, G. Steroids 2010, 75, 513.
8. [8]
  (a) Hogg, J. A. ; Lincoln, F. H. ; Nathan, A. H. ; Hanze, A. R. ; Schneider, W. P. ; Beal, P. F. ; Korman, J. J. Am. Chem. Soc. 1955, 77, 4438.
  (b) Allen, G. R. ; Weiss, M. J. J. Am. Chem. Soc. 1959, 81, 4968.
  (c) Schaub, R. E. ; Allen, G. R. ; Weiss, M. J., J. Am. Chem. Soc. 1959, 81, 4962.
9. [9]
  Larock, R. C.; Hightower, T. R.; Kraus, G. A.; Hahn, P.; Zheng, D. Tetrahedron Lett. 1995, 36, 2423. doi: 10.1016/0040-4039(95)00306-W
10. [10]
  Fryszkowska, A.; Peterson, J.; Davies, N. L. Org. Process Res. Dev. 2016, 20, 1520. doi: 10.1021/acs.oprd.6b00215
11. [11]
  Guo, P. -P.; Ding, K. Tetrahedron Lett. 2015, 56, 4096. doi: 10.1016/j.tetlet.2015.05.026
12. [12]
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