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A new chiral primary–tertiary diamine-Brønsted acid salt organocatalyst for the highly enantioselective direct anti-aldol and syn-Mannich reactions

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Abstract

A new primary–tertiary diamine catalyst is easily prepared in a few steps from inexpensive, commercially available, enantiopure materials. This organocatalyst can be effective catalyzed the direct asymmetric aldol and Mannich reactions. The anti-aldol products can be obtained with up to a 99:1 anti/syn ratio and >98 % ee, while the syn-Mannich products could be obtained with up to a 99:1 syn/anti ratio and >99 % ee. Catalyst 1c can be used efficiently on a large scale with the enantioselectivities of the anti-aldol and syn-Mannich reactions being maintained at the same level, which offers a great possibility for application in industry.

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References

  1. C.H. Heathcock, in Comprehensive Organic Synthesis, vol. 2, ed. by B.M. Trost, I. Fleming, C.H. Heathcock (Pergamon, Oxford, 1991), p. 133

    Chapter  Google Scholar 

  2. E.M. Carreira, E.N. Jacobsen, A. Pfaltz, H. Yamamoto, Comprehensive Asymmetric Catalysis, vol. 3 (Springer, Berlin, 1999), pp. 997–1066

    Google Scholar 

  3. M. Shibasaki, N. Yoshikawa, S. Matsunaga, in Comprehensive Asymmetric Catalysis, ed. by E.N. Jacobsen, A. Pfaltz, H. Yamamoto, Supp. 1 (Berlin, Springer, 2003), pp. 135–142

  4. T.D. Machajewski, C.H. Wong, Angew. Chem. Int. Ed. 39, 1352–1374 (2000)

    Article  CAS  Google Scholar 

  5. H. Heathcock, in Asymmetric Synthesis, ed. by J.D. Morrison, Vol. 3 (New York, Academic, 1984), pp. 111–212

  6. S. Masamune, W. Choy, J.S. Petersen, L.R. Sita, Angew. Chem. Int. Ed. Engl. 24, 1–30 (1985)

    Article  Google Scholar 

  7. L.M. West, P.T. Northcote, J. Org. Chem. 65, 445–449 (2000)

    Article  CAS  Google Scholar 

  8. G. Hçfle, N. Bedorf, H. Steinmetz, D. Schomburg, K. Gerth, H. Reichenbach, Angew. Chem. Int. Ed. Engl. 35, 1567–1569 (1996)

    Article  Google Scholar 

  9. A.K. Ghosh, J. Kass, D.D. Anderson, X.M. Xu, C. Marian, Org. Lett. 10, 4811–4814 (2008)

    Article  CAS  Google Scholar 

  10. S. Raghavan, K. Rathore, Tetrahedron 65, 10083–10092 (2009)

    Article  CAS  Google Scholar 

  11. L.C. Dias, C.D.C.S. Goncalves, Adv. Synth. Catal. 350, 1017–1021 (2008)

    Article  CAS  Google Scholar 

  12. V. Malathong, S.D. Rychnovsky, Org. Lett. 11, 4220–4223 (2009)

    Article  CAS  Google Scholar 

  13. B. List, R.A. Lerner, C.F. Barbas III, J. Am. Chem. Soc. 122, 2395 (2000)

    Article  CAS  Google Scholar 

  14. W. Notz, B. List, J. Am. Chem. Soc. 122, 7386 (2000)

    Article  CAS  Google Scholar 

  15. K. Sakthivel, W. Notz, T. Bui, C.F. Barbas III, J. Am. Chem. Soc. 123, 5260 (2001)

    Article  CAS  Google Scholar 

  16. A. Cordova, W. Notz, C.F. Barbas III, Chem. Commun. 3024 (2002)

  17. B. Alcaide, P. Almendros, Angew. Chem. Int. Ed. 42, 858 (2003)

    Article  CAS  Google Scholar 

  18. B. List, Acc. Chem. Res. 37, 548 (2004)

    Article  CAS  Google Scholar 

  19. W. Notz, F. Tanaka, C.F. Barbas III, Acc. Chem. Res. 37, 580 (2004)

    Article  CAS  Google Scholar 

  20. S. Saito, H. Yamamoto, Acc. Chem. Res. 37, 570 (2004)

    Article  CAS  Google Scholar 

  21. C. Palomo, M. Oiarbide, J.M. GarcSa, Chem. Soc. Rev. 33, 65 (2004)

    Article  CAS  Google Scholar 

  22. S. Mukherjee, Y.W. Yang, S. Hoffmann, B. List, Chem. Rev. 107, 5471 (2007)

    Article  CAS  Google Scholar 

  23. G. Guillena, C. Najera, D.J. Ramon, Tetrahedron Asymmetry 18, 2249 (2007)

    Article  CAS  Google Scholar 

  24. U.M. Lindstrom, Chem. Rev. 102, 2751 (2002)

    Article  Google Scholar 

  25. C.J. Li, Chem. Rev. 105, 3095 (2005)

    Article  CAS  Google Scholar 

  26. Y. Hayashi, T. Sumiya, J. Takahashi, H. Gotoh, T. Urushima, M. Shoji, Angew. Chem. Int. Ed. 45, 958 (2006)

    Article  CAS  Google Scholar 

  27. C.J. Li, L. Chen, Chem. Soc. Rev. 35, 68 (2006)

    Article  Google Scholar 

  28. J. Huang, X. Zhang, D.W. Armstrong, Angew. Chem. Int. Ed. 46, 9073 (2007)

    Article  CAS  Google Scholar 

  29. J.B.F.N. Engberts, M.J. Blandamer, Chem. Commun. 1701 (2001)

  30. N. Akiya, P.E. Savage, Chem. Rev. 102, 2725 (2002)

    Article  CAS  Google Scholar 

  31. S. Kobayashi, K. Manabe, Acc. Chem. Rev. 35, 209 (2002)

    Article  CAS  Google Scholar 

  32. D. Sinou, Adv. Synth. Catal. 344, 221 (2002)

    Article  CAS  Google Scholar 

  33. C.J. Li, T.H. Chan, Organic Reaction in Aqueous Media (Wiley, New York, 1997)

    Google Scholar 

  34. P.A. Grieco, Organic Synthesis in Water (Blackie, London, 1998)

    Book  Google Scholar 

  35. D. Almasi, D.A. Alonso, A.N. Balaguer, C. Nájera, Adv. Synth. Catal. 351, 1123 (2009)

    Article  CAS  Google Scholar 

  36. B. Rodriguez, T. Rantanen, C. Bolm, Angew. Chem. Int. Ed. 45, 6924 (2006)

    Article  CAS  Google Scholar 

  37. B. Rodriguez, A. Bruckmann, C. Bolm, Chem. Eur. J. 13, 4710 (2007)

    Article  CAS  Google Scholar 

  38. Y. Hayashi, S. Aratake, T. Itoh, T. Okano, T. Sumiya, M. Shoji, Chem. Commun. 957 (2007)

  39. G. Guillena, M.C. Hita, C. Nájera, S.F. Viózquez, J. Org. Chem. 73, 5933 (2008)

    Article  CAS  Google Scholar 

  40. A. Bruckmann, A. Krebs, C. Bolm, Green Chem. 10, 1131 (2008)

    Article  CAS  Google Scholar 

  41. G. Guillena, C. Nájera, S.F. Viózquez, Synlett. 3031 (2008)

  42. J.H. Lin, C.P. Zhang, J.C. Xiao, Green Chem. 11, 1750–1753 (2009)

    Article  CAS  Google Scholar 

  43. S. Luo, X.Mi, S. Liu, H. Xu, C.J.P. Heng, Chem. Commun. 3687–3689 (2006)

  44. S. Luo, H. Xu, J. Li, L. Zhang, X. Mi, X. Zheng, J.P. Cheng, Tetrahedron 63, 11307–11314 (2007)

    Article  CAS  Google Scholar 

  45. S.Z. Luo, P.X. Zhou, J.Y. Li, J.P. Cheng, Chem. Eur. J. 16, 4457–4461 (2010)

    Article  CAS  Google Scholar 

  46. S. Luo, H. Xu, L. Zhang, J. Li, J.P. Cheng, Org. Lett. 10, 653–656 (2008)

    Article  CAS  Google Scholar 

  47. S. Luo, H. Xu, J.P. Cheng, Org. Lett. 10, 1775–1778 (2008)

    Article  CAS  Google Scholar 

  48. J. Li, S. Luo, J.P. Cheng, J. Org. Chem. 74, 1747–1750 (2009)

    Article  CAS  Google Scholar 

  49. P.X. Zhou, S.Z. Luo, J.P. Cheng, Org. Biomol. Chem. 9, 1784–1790 (2011)

    Article  CAS  Google Scholar 

  50. M. Shi, W. Zhang, Tetrahedron Asymmetry 14, 3407–3414 (2003)

    Article  CAS  Google Scholar 

  51. Y.Q. Yang, Z. Chai, H.F. Wang, X.K. Chen, H.F. Cui, C.W. Zheng, H. Xiao, P. Li, G. Zhao, Chem. Eur. J. 15, 13295–13298 (2009)

    Article  CAS  Google Scholar 

  52. B. List, J. Am. Chem. Soc. 122, 9336 (2000)

    Article  CAS  Google Scholar 

  53. B. List, P. Pojarliev, W.T. Biller, H. Martin, J. Am. Chem. Soc. 124, 827 (2002)

    Article  CAS  Google Scholar 

  54. N.S. Chowdari, M. Ahmad, K. Albertshofer, F. Tanaka III, C.F. Barbas, Org. Lett. 8, 2839 (2006)

    Article  CAS  Google Scholar 

  55. J.F. Zheng, Y.X. Li, S.Q. Zhang, X.M. Wang, S.T. Yang, J. Bai, F. Wang, G.L. Zhang, F.A. Liu, Acta Chim. Sinica 65, 553 (2007)

    CAS  Google Scholar 

  56. X. Zhang, Y.B. Qian, Y.M. Wang, Eur. J. Org. Chem. 3, 515–522 (2010)

    Article  Google Scholar 

  57. Q. Gu, L.X. Jiang, K. Yuan, L. Zhang, X.Y. Wu, Synth. Commun. 38, 4198–4206 (2008)

    Article  CAS  Google Scholar 

  58. I. Ibrahem, W. Zou, M. Engqvist, Y. Xu, Chem. Eur. J. 11, 7024 (2005)

    Article  CAS  Google Scholar 

  59. S.S.V. Ramasastry, H. Zhang, F. Tanaka III, C.F. Barbas, J. Am. Chem. Soc. 129, 288 (2007)

    Article  CAS  Google Scholar 

  60. L. Cheng, X. Wu, Y. Lu, Org. Biomol. Chem. 5, 1018 (2007)

    Article  CAS  Google Scholar 

  61. S. ueki, T. Igarashi, T. Nakajima, I. Shimizu, Chem. Lett. 35, 682–683 (2006)

    Article  Google Scholar 

  62. N. Dirvianskyte, J. Straukas, V. Razumas, E. Butkus, J. Biosci. 58, 366–370 (2003)

    CAS  Google Scholar 

  63. L.L. Cheng, X. Han, H.M. Huang, M.W. Wonga, Y.X. Lu, Chem. Commun. 4143–4145 (2007)

  64. F.Z. Peng, Z.H. Shao, X.W. Pu, H.B. Zhang, Adv. Synth. Catal. 350, 2199 (2008)

    Article  CAS  Google Scholar 

  65. M. Kaik, J. Gawroński, Tetrahedron Asymmetry 14, 155 (2003)

    Article  Google Scholar 

  66. A. Berkessel, S. Mukherjee, T.N. Müllee, F. Cleemann, K. Roland, M. Brandenburg, J.M. Neudörfl, Lex, J. Org. Biomol. Chem. 4, 4319 (2006)

    Article  CAS  Google Scholar 

  67. C.L. Wu, X.K. Fu, X.B. Ma, S. Li, Tetrahedron Asymmetry 21, 2465–2470 (2010)

    Article  CAS  Google Scholar 

  68. C.L. Wu, X.K. Fu, X.B. Ma, S. Li, C. Li, Tetrahedron Lett. 51, 5775–5777 (2010)

    Article  CAS  Google Scholar 

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Acknowledgment

Authors are grateful to Southwest University of China for financial support.

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Authors and Affiliations

  1. College of Chemistry and Chemical Engineering, Research Institute of Applied Chemistry Southwest University, The Key Laboratory of Applied Chemistry of Chongqing Municipality, Chongqing, China

    Guodong Chen, Xiangkai Fu, Chuanlong Wu & Chao Li

  2. Chongqing Unis Chemical Co, Ltd, Chongqing, 402161, China

    Chuanlong Wu

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  1. Guodong Chen
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  2. Xiangkai Fu
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Correspondence to Xiangkai Fu.

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Chen, G., Fu, X., Wu, C. et al. A new chiral primary–tertiary diamine-Brønsted acid salt organocatalyst for the highly enantioselective direct anti-aldol and syn-Mannich reactions. Res Chem Intermed 39, 1069–1087 (2013). https://doi.org/10.1007/s11164-012-0667-x

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