Citation: Guo Qingjun. Asymmetric Synthesis of Diarylmethanols by Chiral Phosphoramide Ligands Catalysts[J]. Chinese Journal of Organic Chemistry, ;2019, 39(10): 2912-2919. doi: 10.6023/cjoc201902026 shu

Asymmetric Synthesis of Diarylmethanols by Chiral Phosphoramide Ligands Catalysts

Guo Qingjun ^,

Key Laboratory of Inorganic Chemistry in Universities of Shandong, Department of Chemistry and Chemical Engineering, Jining University, Qufu 273155, Shandong

Corresponding author: Guo Qingjun, guoqingjun2005@126.com
Received Date: 24 February 2019
Revised Date: 29 March 2019
Available Online: 21 October 2019

Figures(3)

In order to improve the application of chiral phosphoramide ligands in catalytic asymmetric reactions, thiophosphoramide, which was synthesized from trans-1, 2-cyclohexanediamine was used as a catalyst to synthesize chiral diarylmethanol compounds through addition reaction. The catalytic activity of the ligand in the asymmetric addition reaction of the arylalkyl zincs to the aromatic aldehyde can be as high as 94% ee under the optimized reaction conditions in the presence of 30 mol% phosphoramide ligand N-((1R, 2R)-2-(isopropylamino)cyclohexyl)-P, P-diphenylphosphinic amide (9c) and the corresponding chiral diarylmethanol compound was obtained with the yields of >90%. Despite the large amount of catalyst, the ligand is very convenient to recycle and reuse in this system. At the same time, the reaction mechanism was speculated, and it is believed that the quaternary transition state and the six-element transition state formed by the reaction process are beneficial to improve the enantioselectivity of the reaction.
- chiral thiophosphoramide ligand,
- diarylmethanols,
- asymmetric catalysis
1. [1]
  Einhorn, A. Ber. Dtsch. Chem. Ges. 1883, 16, 2208. doi: 10.1002/cber.188301602132
2. [2]
  Torrens, A.; Castrillo, J.; Claparols, A.; Redondo, J. Synlett 1999, 765.
3. [3]
  (a) Casy, A. F.; Drake, A. F.; Ganellin, C. R.; Mercer, A. D.; Upton, C. Chirality 1992, 4, 356.
  (b) Müller, P.; Nury, P.; Bernardinelli, G. Eur. J. Org. Chem. 2001, 2001, 4137.
4. [4]
  Hite, G.; Barouh, V.; Dall, H.; Patel, D. J. Med. Chem. 1971, 14, 834. doi: 10.1021/jm00291a014
5. [5]
  Guo, Z.; Raeissi, S.; White, R. B.; Stevens, J. C. Drug Metab. Dispos. 1997, 25, 390.
6. [6]
  Li, C.; Chauret, N.; Trimble, L. A.; Nicoll-Griffith, D. A; Silva, J. M; MacDonald, D.; Perrier, H.; Yergey, J. A.; Parton, T.; Alexander, R. P.; Warrellow, G. J. Drug Metab. Dispos. 2001, 29, 232.
7. [7]
  (a) James, M. N. G.; Williams, G. J. B. Can. J. Chem. 1974, 52, 1872.
  (b) Shafi'ee, A.; Hite, G. J. Med. Chem. 1969, 12, 266.
8. [8]
  (a) Bolm, C.; Hildebrand, J. P.; Muñiz, K.; Hermanns, N. Angew. Chem., Int. Ed. 2001, 40, 3284.
  (b) Ji, J. X.; Wu, J.; Xu, L. J.; Chiu, W. Y.; Kim, H. L.; Albert, S. C. Pure Appl. Chem. 2006; 78, 267.
9. [9]
  (a) Fernández-Mateos, E.; Maciá, B.; Yus, M. Tetrahedron: Asymmetry 2012, 23, 789.
  (b) Wu, K. H.; Gau, H. M. J. Am. Chem. Soc. 2006, 128, 14808.
10. [10]
  (a) Da, C.-S.; Wang, J. R.; Yin, X. G.; Fan, X. Y.; Liu, Y.; Yu, S. L. Org. Lett. 2009, 11, 5578.
  (b) Fan, X. Y.; Yang, Y. X.; Zhuo, F.-F.; Yu, S. L.; Li, X.; Guo, Q. P.; Du, Z. X.; Da, C. S. Chem. -Eur. J. 2010, 16, 7988.
11. [11]
  Tomita, D.; Wada, R.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc. 2005, 127, 4138. doi: 10.1021/ja0507362
12. [12]
  Chang, S. J.; Zhou, S.; Gau, H. M. RSC Adv. 2015, 5, 9368. doi: 10.1039/C4RA14173C
13. [13]
  (a) Fernández-Mateos, E.; Maciá, B.; Yus, M. Eur. J. Org. Chem. 2012, 3732.
  (b) Nakagawa, Y.; Muramatsu, Y.; Harada, T. Eur. J. Org. Chem. 2010, 6535.
14. [14]
  Bolm, C.; Rudolph, J. J. Am. Chem. Soc. 2002, 124, 14850. doi: 10.1021/ja028518l
15. [15]
  Bauer, M.; Maurer, F.; Hoffmann, S. M.; Kazmaier U. Synlett 2008, 3203.
16. [16]
17. [17]
  Huang, H.; Bian, G.; Zong, H.; Wang, Y.; Yang, S.; Yue, H.; Song, L.; Fan, H. Org. Lett. 2016, 18, 2524. doi: 10.1021/acs.orglett.6b00088
18. [18]
  Shen, B.; Huang, H.; Bian, G.; Zong, H.; Song, L. Chirality 2013, 25, 561. doi: 10.1002/chir.22171
19. [19]
  Huang, H. Y.; Zong, H.; Shen, B.; Yue, H. F.; Bian, G. L.; Song, L. Tetrahedron 2014, 70, 1289. doi: 10.1016/j.tet.2013.12.054
20. [20]
  Kaik, M.; Gawroński, J. Tetrahedron:Asymmetry 2003 141559.
21. [21]
  Huang, H. Y.; Z ong, H.; Bian, G. L.; Song, L. J. Org. Chem. 2012, 77, 10427. doi: 10.1021/jo3016715
22. [22]
  Yang, Y. X.; Liu, Y.; Zhang, L.; Jia, Y. E.; Wang, P.; Zhuo, F. F.; An, X. T.; Da, C. S. J. Org. Chem. 2014, 79, 10696. doi: 10.1021/jo502070r
23. [23]
  Wu, X. Y.; Liu, X. Y.; Zhao, G. Tetrahedron:Asymmetry 2005, 16, 2299. doi: 10.1016/j.tetasy.2005.06.010
24. [24]
  Tian, C.; Gong, L.; Meggers, E. Chem. Commun. 2016, 52, 4207. doi: 10.1039/C6CC00972G
25. [25]
  Barsamian, A. L.; Wu, Z. H.; Blakemore, P. R. Org. Biomol. Chem. 2015, 13, 3781. doi: 10.1039/C5OB00159E
26. [26]
  Wang, Y. B.; Zong, H.; Huang, H. Y.; Song, L. Tetrahedron:Asymmetry 2017, 28, 90. doi: 10.1016/j.tetasy.2016.11.011
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