Citation: Sheng-Jian Jia, Da-Ming Du. Enantioselective chlorination ofb-keto esters and amides catalyzed by chiral copper(Ⅱ) complexes of squaramide-linked bisoxazoline ligand[J]. Chinese Chemical Letters, ;2014, 25(11): 1479-1484. doi: 10.1016/j.cclet.2014.06.023 shu

Enantioselective chlorination ofb-keto esters and amides catalyzed by chiral copper(Ⅱ) complexes of squaramide-linked bisoxazoline ligand

Sheng-Jian Jia ,
Da-Ming Du ^,

1.
School of Chemical Engineering and Environment, Beijing Institute of Technology, Beijing 100081, China

Corresponding author: Da-Ming Du,
Received Date: 24 April 2014
Available Online: 12 June 2014
Fund Project:

Enantioselective chlorination of β-keto esters and amides catalyzed by squaramide-linked bisoxazoline ligand-Cu(OAc)₂ complexes was investigated. The corresponding chlorinated products were obtained in excellent yields with moderate enantioselectivities. The effect of solvent, temperature, Lewis acid, and ligand structure on the reaction is discussed. This was the first investigation of catalytic asymmetric α-chlorination of β-keto amides. This study has highlighted that a simple chiral squaramide-oxazoline with cheap Cu(OAc)₂·H₂O complexes can catalyze this chlorination.
- Asymmetric catalysis,
- Bisoxazoline,
- Squaramide,
- Chlorination,
- β-Keto esters
1. [1]
  [1] N.D. Kimpe, R. Verhé , The Chemistry of a-Halo-ketones, a-Haloaldehydes, and a- Haloimines, John Wiley & Sons, New York, 1988.
2. [2]
  [2] R.C. Larock, Comprehensive Organic Transformations, 2nd ed., Wiley-VCH, New York, 1999.
3. [3]
  [3] G. Thomas, Medicinal Chemistry: An Introduction, Wiley, New York, 2000.
4. [4]
  [4] H. Ibrahim, A. Togni, Enantioselective halogenation reactions, Chem. Commun. (2004) 1147-1155.
5. [5]
  [5] J.A. Ma, D. Cahard, Asymmetric fluorination, trifluoromethylation, and perfluoroalkylation reactions, Chem. Rev. 104 (2004) 6119-6146.
6. [6]
  [6] K. Muñ iz, Improving enantioselective fluorination reactions: chiral N-fluoroammonium salts and transition metal catalysts, Angew. Chem. Int. Ed. 40 (2001) 1653-1656.
7. [7]
  [7] S. France, A. Weatherwax, T. Lectka, Recent developments in catalytic, asymmetric a-halogenation: a new frontier in asymmetric catalysis, Eur. J. Org. Chem. (2005) 475-479.
8. [8]
  [8] M. Oestreich, Strategies for catalytic asymmetric electrophilic a-halogenation of carbonyl compounds, Angew. Chem. Int. Ed. 44 (2005) 2324-2327.
9. [9]
  [9] A.M.R. Smith, K.K. Hii, Transition metal catalyzed enantioselective a-heterofunctionalization of carbonyl compounds, Chem. Rev. 111 (2011) 1637-1656.
10. [10]
  [10] G. Guillena, D.J. Ramon, Enantioselective a-heterofunctionalisation of carbonyl compounds: organocatalysis is the simplest approach, Tetrahedron 17 (2006) 1465-1492.
11. [11]
  [11] M. Ueda, T. Kano, K. Maruoka, Organocatalyzed direct asymmetric a-halogenation of carbonyl compounds, Org. Biomol. Chem. 7 (2009) 2005-2012.
12. [12]
  [12] L. Hintermann, A. Togni, Catalytic enantioselective chlorination and bromination of b-keto esters, Helv. Chim. Acta 83 (2000) 2425-2435.
13. [13]
  [13] H. Ibrahim, F. Kleinbeck, A. Togni, Catalytic asymmetric chlorination of b-keto esters with hypervalent iodine compounds, Helv. Chim. Acta 87 (2004) 605-610.
14. [14]
  [14] M. Marigo, N. Kumaragurubaran, K.A. Jøgensen, Catalytic asymmetric bromination and chlorination of b-ketoesters, Chem. Eur. J. 10 (2004) 2133-2137.
15. [15]
  [15] J. Li, W. Pan, Z. Wang, X. Zhang, K. Ding, Access to both enantiomers of a-chloro-bketo esters with a single chiral ligand: highly efficient enantioselective chlorination of cyclic b-keto esters catalyzed by chiral copper(Ⅱ) and zinc(Ⅱ) complexes of a spiro-2,20-bischroman-based bisoxazoline ligand, Adv. Synth. Catal. 354 (2010) 1980-1986.
16. [16]
  [16] N. Shibata, J. Kohno, K. Takai, T. Ishimaru, S. Nakamura, T. Toru, S. Kanemasa, Highly enantioselective catalytic fluorination and chlorination reactions of carbonyl compounds capable of two-point binding, Angew. Chem. Int. Ed. 44 (2005) 4204-4207.
17. [17]
  [17] M. Frings, C. Bolm, Enantioselective halogenation of b-oxo esters catalyzed by a chiral sulfoximine-copper complex, Eur. J. Org. Chem. (2009) 4085- 4090.
18. [18]
  [18] M.-H. Qi, F.J. Wang, M. Shi, Synthesis of novel chiral oxazoline-Schiff base ligands for the catalytic asymmetric chlorination of b-keto esters, Tetrahedron 21 (2010) 247-253.
19. [19]
  [19] M. Kawatsura, S. Hayashi, Y. Komatsu, S. Hayase, T. Itoh, Enantioselective a-fluorination and chlorination of b-ketoesters by cobalt catalyst, Chem. Lett. 39 (2010) 466-467.
20. [20]
  [20] G. Bartoli, M. Bosco, A. Carlone, M. Locatelli, P. Melchiorre, L. Sambri, Organocatalytic, asymmetric a-halogenation of 1,3-dicarbonyl compounds, Angew. Chem. Int. Ed. 44 (2005) 6219-6222.
21. [21]
  [21] Y. Cai, W. Wang, K. Shen, et al., Highly enantioselective a-chlorination of cyclic b-ketoesters catalyzed by N,N0-dioxide using NCS as the chlorine source, Chem. Commun. 46 (2010) 1250-1252.
22. [22]
  [22] P. Etayo, R. Badorrey, M.D. Diaz-de-Villegas, Chiral amino diol derivatives as new modular organocatalysts for the enantioselective a-chlorination of cyclic b-keto esters, Adv. Synth. Catal. 352 (2010) 3329-3338.
23. [23]
  [23] J.S. Johnson, D.A. Evans, Chiral bis(oxazoline) copper(Ⅱ) complexes: versatile catalysts for enantioselective cycloaddition, aldol, Michael, and carbonyl ene reactions, Acc. Chem. Res. 33 (2000) 325-335.
24. [24]
  [24] D. Rechavi, M. Lemaire, Enantioselective catalysis using heterogeneous bis(oxazoline) ligands: which factors influence the enantioselectivity, Chem. Rev. 102 (2002) 3467-3493.
25. [25]
  [25] J. Zhou, Y. Tang, The development and application of chiral trisoxazolines in asymmetric catalysis and molecular recognition, Chem. Soc. Rev. 34 (2005) 664-676.
26. [26]
  [26] G. Desimoni, G. Faita, K.A. Jørgensen, C2-Symmetric chiral bis(oxazoline) ligands in asymmetric catalysis, Chem. Rev. 106 (2006) 3561-3651.
27. [27]
  [27] H. Nishiyama, Synthesis and use of bisoxazolinyl-phenyl pincers, Chem. Soc. Rev. 36 (2007) 1133-1141.
28. [28]
  [28] G.C. Hargaden, P.J. Guiry, Recent applications of oxazoline-containing ligands in asymmetric catalysis, Chem. Rev. 109 (2009) 2505-2550.
29. [29]
  [29] J.P. Malerich, K. Hagihara, V.H. Rawal, Chiral squaramide derivatives are excellent hydrogen bond donor catalysts, J. Am. Chem. Soc. 130 (2008) 14416-14417.
30. [30]
  [30] Y. Zhu, J.P. Malerich, V.H. Rawal, Squaramide-catalyzed enantioselective Michael addition of diphenyl phosphite to nitroalkenes, Angew. Chem. Int. Ed. 49 (2010) 153-156.
31. [31]
  [31] Y. Qian, G. Ma, A. Lv, et al., Squaramide-catalyzed enantioselective Friedel-Crafts reaction of indoles with imines, Chem. Commun. 46 (2010) 3004-3006.
32. [32]
  [32] W. Yang, D.M. Du, Highly enantioselective Michael addition of nitroalkanes to chalcones using chiral squaramides as hydrogen bonding organocatalysts, Org. Lett. 12 (2010) 5450-5453.
33. [33]
  [33] W. Yang, D.M. Du, Chiral squaramide-catalyzed highly enantioselective Michael addition of 2-hydroxy-1,4-naphthoquinones to nitroalkenes, Adv. Synth. Catal. 353 (2011) 1241-1246.
34. [34]
  [34] W. Yang, D.M. Du, Chiral squaramide-catalyzed highly diastereo-and enantioselective direct Michael addition of nitroalkanes to nitroalkenes, Chem. Commun. 47 (2011) 12706-12708.
35. [35]
  [35] C. Min, X. Han, Z.Q. Liao, et al., C3-Symmetrical cinchonine-squaramide as new highly efficient, and recyclable organocatalyst for enantioselective Michael addition, Adv. Synth. Catal. 353 (2011) 2715-2720.
36. [36]
  [36] H.Y. Bae, S. Some, J.H. Lee, et al., Organocatalytic enantioselective Michaeladdition of malonic acid half-thioesters to b-nitroolefins: from mimicry of polyketide synthases to scalable synthesis of g-amino acids, Adv. Synth. Catal. 353 (2011) 3196-3202.
37. [37]
  [37] D.M. Du, S.F. Lu, T. Fang, J. Xu, Asymmetric Henry reaction catalyzed by C2- symmetric tridentate bis(oxazoline) and bis(thiazoline) complexes: metal-controlled reversal of enantioselectivity, J. Org. Chem. 70 (2005) 3712-3715.
38. [38]
  [38] S.F. Lu, D.M. Du, Asymmetric conjugate addition of nitroalkanes to nitroalkenes catalyzed by C2-symmetric tridentate bis(oxazoline) and bis(thiazoline) zinc complexes, J. Am. Chem. Soc. 128 (2006) 7418-7419.
39. [39]
  [39] S.F. Lu, D.M. Du, J. Xu, Enantioselective Friedel-Crafts alkylation of indoles with nitroalkenes catalyzed by bifunctional tridentate bis(oxazoline)-Zn(Ⅱ) complex, Org. Lett. 8 (2006) 2115-2118.
40. [40]
  [40] H. Liu, J. Xu, D.M. Du, Asymmetric Friedel-Crafts alkylation of methoxyfuran with nitroalkenes catalyzed by diphenylamine-tethered bis(oxazoline)-Zn(Ⅱ) complexes, Org. Lett. 9 (2007) 4725-4728.
41. [41]
  [41] H. Liu, S.F. Lu, J. Xu, D.M. Du, Asymmetric Friedel-Crafts alkylation of electron-rich N-heterocycles with nitroalkenes catalyzed by diphenylamine-tethered bis(oxazoline) and bis(thiazoline)-Zn(Ⅱ) complexes, Chem. Asian J. 3 (2008) 1111- 1121.
42. [42]
  [42] H. Liu, D.M. Du, Immobilization of diphenylamine-linked bis(oxazoline) ligands and their application in the asymmetric Friedel-Crafts alkylation of indole derivatives with nitroalkenes, Eur. J. Org. Chem. (2010) 2121-2131.
43. [43]
  [43] W. Yang, H. Liu, D.M. Du, Efficient in situ three-component formation of chiral oxazoline-Schiff base copper(Ⅱ) complexes: towards combinatorial library of chiral catalysts for asymmetric Henry reaction, Org. Biomol. Chem. 8 (2010) 2956-2960.
44. [44]
  [44] J. Peng, D.M. Du, Asymmetric Friedel-Crafts alkylation of indoles with nitrodienes and 2-propargyloxy-β-nitrostyrenes catalyzed by diphenylamine-linked bis(oxazoline)- Zn(OTf)2 complexes, Eur. J. Org. Chem. (2012) 4042-4051.
45. [45]
  [45] B. Fu, D.M. Du, Q. Xia, Convenient synthesis of bis(oxazoline) dicarboxylate derivatives, Chin. Chem. Lett. 15 (2004) 383-385.
46. [46]
  [46] S.J. Jia, D.M. Du, Enantioselective Friedel-Crafts alkylation of indoles with b,gunsaturated a-ketoesters catalysed by new squaramide-linked bisoxazoline- Zn(OTf)2 complexes, Tetrahedron: Asymmetry (2014), http://dx.doi.org/10.1016/ j.tetasy.2014.05.011.
47. [47]
  [47] J. Xu, Influence of the electronic effect of catalysts on the enantioselectivity: applicability and complexity, Curr. Org. Synth. 7 (2010) 650-676.
48. [48]
  [48] L. Ma, P. Jiao, Q. Zhang, J. Xu, Rigid backbone 1,8-anthracene-linked bis-oxazolines (AnBOXes): design, synthesis, application and characteristics in catalytic asymmetric aziridination, Tetrahedron 16 (2005) 3718-3734.
49. [49]
  [49] L. Ma, P. Jiao, Q. Zhang, D.M. Du, J. Xu, Ligand and substrate p-stacking interaction controlled enantioselectivity in the asymmetric aziridination, Tetrahedron 18 (2007) 878-884.
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