Citation: Guilan He, Yaofeng Yuan. 手性二茂铁双膦配体Xyliphos的合成及应用[J]. University Chemistry, ;2025, 40(8): 130-137. doi: 10.12461/PKU.DXHX202409122 shu

手性二茂铁双膦配体Xyliphos的合成及应用

Guilan He ,
Yaofeng Yuan ^,

College of Chemistry, Fuzhou University, Fuzhou 350108, China

Corresponding author: Yaofeng Yuan, yaofeng_yuan@fzu.edu.cn
Received Date: 27 September 2024
Revised Date: 26 December 2024

手性二茂铁双膦配体广泛应用在不对称催化领域，其中最著名的是Xyliphos配体，其铱络合物催化剂用于手性除草剂(S)-异丙甲草胺生产工艺中关键中间体MEA (2-methyl-6-ethylaniline，2-甲基-6-乙基苯胺)-亚胺不对称氢化反应，催化工艺效率十分高，能完成多于2000000的周转率，年生产量大于10000吨，是规模最大的对映选择性催化工艺。Xyliphos的合成及在工业上的成功应用使其成为基础研究到工业化应用的典型案例，意义重大，影响深远。
- Chiral,
- Ferrocene,
- Phosphine ligand,
- Metolachlor
1. [1]
  Young, J. F.; Osborn, J. A.; Jardine, F. H.; Wilkinson, G. Chem. Comm. 1965, No. 7, 131.
2. [2]
  Knowles, W. S.; Sabacky, M. J. Chem. Comm. 1968, No. 22, 1445.
3. [3]
  Horner, L.; Siegel, H.; Büthe, H. Angew. Chem. Int. Ed. 1968, 7 (12), 942.
4. [4]
  Knowles, W. S.; Sabacky, M. J.; Vineyard, B. D.; Weinkauff, D. J. J. Am. Chem. Soc. 1975, 97 (9), 2567.
5. [5]
  Dang, T. P.; Kagan, H. B. J. Am. Chem. Soc. 1971, No. 10, 481.
6. [6]
  Kagan, H. B.; Dang, T. P. J. Am. Chem. Soc. 1972, 94 (18), 6429.
7. [7]
  Vineyard, B. D.; Knowles, W. S.; Sabacky, M. J.; Bachman, G. L.; Weinkauff, D. J. J. Am. Chem. Soc. 1977, 99 (18), 5946.
8. [8]
  Miyashita, A.; Yasuda, A.; Takaya, H.; Toriumi, K.; Ito, T.; Souchi, T.; Noyori, R. J. Am. Chem. Soc. 1980, 102 (27), 7932.
9. [9]
  Togni, A.; Breutel, C.; Schnyder, A.; Spindler, F.; Landert, H.; Tijani, A. J. Am. Chem. Soc. 1994, 116 (9), 4062.
10. [10]
  Albert, S. C. C.; Hu, W. H.; Pai, C. C.; Lau, C. P.; Jiang, Y. Z.; Mi, A. Q.; Yan, M.; Sun, J.; Lou, R. L.; Deng, J. G. J. Am. Chem. Soc. 1997, 119 (40), 9570.
11. [11]
12. [12]
13. [13]
  Katja, H.; Heinrich, L. Organometallics 2013, 32(20), 5623.
14. [14]
  Special Issue: Ferrocene. J. Organomet. Chem. 2001, 637–639, 1.
15. [15]
  Stepnicka, P. Ferrocenes: Ligands, Materials and Biomolecules; John Wiley and Sons: England, UK, 2008; pp. 1–237.
16. [16]
  Togni, A.; Hayashi, T. Ferrocenes: Homogeneous Catalysis, Organic Synthesis, Materials Science; VCH: New York, NY, USA, 1994; pp. 1–540.
17. [17]
18. [18]
  Gómez Arrayás, R.; Adrio, J.; Carretero, J. C. Angew. Chem. Int. Ed. 2006, 45 (46), 7674.
19. [19]
20. [20]
  Hayashi, T.; Mise, T.; Fukushima, M.; Kagotani, M.; Nagashima, N.; Hamada, Y.; Matsumoto, A.; Kawakami, S.; Konishi, M.; Yamamoto, K. Bull. Chem. Soc. Jpn. 1980, 53 (4), 1138.
21. [21]
  Blaser, H. U.; Pugin, B.; Spindler, F. Helv. Chim. Acta 2021, 104 (1), e2000192.
22. [22]
  Togni, A.; Breutel, C.; Schnyder, A.; Spindler, F.; Landert, H.; Tijani, A. J. Am. Chem. Soc. 1994, 116(9), 4066.
23. [23]
  Spindler, F.; Wirt-Tijani, A.; Landert, H. Ferrocene Diphos-Phines as Ligands for Homogeneous Catalysts. US Patent 5565594, 1995.
24. [24]
25. [25]
  Kwan, A. L.; Morris, R. H. Molecules 2022, 27(16), 5106.
26. [26]
  Gokel, G. W.; Ugi, I. K. J. Chem. Educ. 1972, 49 (4), 294.
27. [27]
  Richards, J. H.; Hill, E. A. J. Am. Chem. Soc. 1959, 81 (13), 3484.
28. [28]
  Gleiter, R.; Bleiholder, C.; Rominger, F. Organometallics 2007, 26 (20), 4850.
29. [29]
  Wright, J.; Frambes, L.; Reeves, P. J. Organomet. Chem. 1994, 476 (2), 215.
30. [30]
  Blaser, H. U.; Spindler, F.; Studer, M. Appl. Catal. A-Gen. 2001, 221 (1), 119.
31. [31]
  Lam, W. S.; Stanton, H. L. K.; Terry, T. L. A. Y.; Wu, J.; Cheung, H. Y.; Lam, F. L.; Yeung, C. H.; Albert, S. C. C. Adv. Synth. Catal. 2006, 348 (3), 370.
32. [32]
  Cabré, A.; Verdaguer, X.; Riera, A. Chem. Rev. 2022, 122 (1), 269.
33. [33]
  Zhao, D. B.; Frank, G. Angew. Chem. Int. Ed. 2013, 52, 9616.
34. [34]
  Wiedner, E. S.; Chambers, M. B.; Pitman, C. L.; Bullock, R. M.; Miller, A. J. M.; Appel, A. M. Chem. Rev. 2016, 116, 8655.
35. [35]
  Chen, M. W.; Ji, Y.; Wang, J.; Chen, Q. A.; Shi, L.; Zhou, Y. G. Org. Lett. 2017, 19 (18), 4988.
36. [36]
  Kim, A. N.; Ngamnithiporn, A.; Welin, E. R.; Daiger, M. T.; Grünanger, C. U.; Bartberger, M. D.; Virgil, S. C.; Stoltz, B. M. ACS Catal. 2020, 10 (5), 3241.
37. [37]
  Welin, E. R.; Ngamnithiporn, A.; Klatte, M.; Lapointe, G.; Pototschnig, G. M.; McDermott, M. S. J.; Conklin, D.; Gilmore, C. D.; Tadross, P. M.; Haley, C. K.; et al. Science 2019, 363 (6424), 270.
38. [38]
  Cuevas, C.; Francesch, A. Nat. Prod. Rep. 2009, 26 (3), 322.
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