DMAP-catalyzed cyanation of aldehydes and ketones with ethyl cyanoformate

Tetrahedron Letters

Volumn 51, Issue 27, 2010, Pages 3547-3549

  Aoki, Shohei ^a   Kotani, Shunsuke ^a   Sugiura, Masaharu ^a   Nakajima, Makoto ^a  

^a KUMAMOTO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

4 DIMETHYLAMINOPYRIDINE; ALDEHYDE; CARBONIC ACID DERIVATIVE; FORMIC ACID DERIVATIVE; KETONE;

ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; CYANATION;

EID: 77954242937     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2010.04.123     Document Type: Article

References (59)

1. For recent reviews on synthesis and reactions of cyanohydrins, see: M. North Synlett 1993 807 820
2. R.J.H. Gregory Chem. Rev. 99 1999 3649 3682
3. M. North Tetrahedron: Asymmetry 14 2003 147 176
4. J.-M. Brunel, and I.P. Holmes Angew. Chem., Int. Ed. 43 2004 2752 2778
5. F.-X. Chen, and X. Feng Synlett 2005 892 899
6. For recent asymmetric cyanations, see: Y. Hamashima, D. Sawada, M. Kanai, and M. Shibasaki J. Am. Chem. Soc. 121 1999 2641 2642
7. M. Kanai, Y. Hamashima, and M. Shibasaki Tetrahedron Lett. 41 2000 2405 2409
8. Y. Hamashima, M. Kanai, and M. Shibasaki J. Am. Chem. Soc. 122 2000 7412 7413
9. Y. Hamashima, M. Kanai, and M. Shibasaki Tetrahedron Lett. 42 2001 691 694
10. Y. Hamashima, D. Sawada, H. Nogami, M. Kanai, and M. Shibasaki Tetrahedron 57 2001 805 814
11. S.-K. Tian, and L. Deng J. Am. Chem. Soc. 123 2001 6195 6196
12. J. Tian, N. Yamagiwa, S. Matsunaga, and M. Shibasaki Angew. Chem., Int. Ed. 41 2002 3636 3638
13. J. Casas, C. Nájera, J.M. Sansano, and J.M. Saá Org. Lett. 4 2002 2589 2592
14. Y.N. Belokon, A.J. Blacker, L.A. Clutterbuck, and M. North Org. Lett. 5 2003 4505 4507
15. S.-K. Tian, R. Hong, and L. Deng J. Am. Chem. Soc. 125 2003 9900 9901
16. J. Casas, A. Baeza, J.M. Sansano, C. Nájera, and J.M. Saá Tetrahedron: Asymmetry 14 2003 197 200
17. J. Tian, N. Yamagiwa, S. Matsunaga, and M. Shibasaki Org. Lett. 5 2003 3021 3024
18. Y. Abiko, N. Yamagiwa, M. Sugita, J. Tian, S. Matsunaga, and M. Shibasaki Synlett 2004 2434 2436
19. N. Yamagiwa, J. Tian, S. Matsunaga, and M. Shibasaki J. Am. Chem. Soc. 127 2005 3413 3422
20. S. Lundgren, E. Wingstrand, M. Penhoat, and C. Moberg J. Am. Chem. Soc. 127 2005 11592 11593
21. M. Hatano, T. Ikeno, T. Miyamoto, and K. Ishihara J. Am. Chem. Soc. 127 2005 10776 10777
22. W. Wentao, G. Shaohua, L. Xiaohua, and F. Xiaoming Synlett 2007 2875 2878
23. S. Gou, J. Wang, X. Liu, W. Wang, F.-X. Chen, and X. Feng Adv. Synth. Catal. 349 2007 343 349
24. R. Chinchilla, C. Nájera, and F.J. Ortega Tetrahedron: Asymmetry 19 2008 265 268
25. M. Hatano, T. Ikeno, T. Matsumura, S. Torii, and K. Ishihara Adv. Synth. Catal. 350 2008 1776 1780
26. N.H. Khan, S. Agrawal, R.I. Kureshy, S.H.R. Abdi, K.J. Prathap, and R.V. Jasra Eur. J. Org. Chem. 2008 4511 4515
27. R. Chinchilla, C. Nájera, F.J. Ortega, and S. Tari Tetrahedron: Asymmetry 20 2009 2279 2286
28. J. Wang, W. Wang, W. Li, X. Hu, K. Shen, C. Tan, X. Liu, and X. Feng Chem. Eur. J. 15 2009 11642 11659
29. N.H. Khan, S. Agrawal, R.I. Kureshy, S.H.R. Abdi, K. Pathak, and H.C. Bajaj Chirality 22 2010 153 158
30. For cyanations with trimethylsilyl cyanide, see: D.A. Evans, L.K. Truesdale, and G.L. Carroll J. Chem. Soc., Chem. Commun. 1973 55 56
31. D.A. Evans, and L.K. Truesdale Tetrahedron Lett. 49 1973 4929 4932
32. S. Kobayashi, Y. Tsuchiya, and T. Mukaiyama Chem. Lett. 20 1991 537 540
33. S. Kobayashi, Y. Tsuchiya, and T. Mukaiyama Chem. Lett. 20 1991 541 544
34. M. Golinski, C.P. Brock, and D.S. Watt J. Org. Chem. 58 1993 159 164
35. P. Saravanan, R.V. Anand, and V.K. Singh Tetrahedron Lett. 39 1998 3823 3824
36. M. Bandini, P.G. Cozzi, P. Melchiorre, and A. Umani-Ronchi Tetrahedron Lett. 42 2001 3041 3043
37. R. Córdoba, and J. Plumet Tetrahedron Lett. 44 2003 6157 6159
38. F. Chen, X. Feng, B. Qin, G. Zhang, and Y. Jiang Org. Lett. 5 2003 949 952
39. I. Amurrio, R. Córdoba, A.G. Csaky, and J. Plumet Tetrahedron 60 2004 10521 10524
40. F.-X. Chen, M.A. Wolfert, J.N. Moore, and G.-J. Boons Chem. Eur. J. 10 2004 4790 4797
41. X.H. Liu, B. Qin, X. Zhou, B. He, and X.M. Feng J. Am. Chem. Soc. 127 2005 8964 8965
42. B. Qin, Liu, Xiaohua, J. Shi, K. Zheng, H. Zhao, and X. Feng J. Org. Chem. 72 2007 2374 2378
43. X. Wang, and S.-K. Tian Tetrahedron Lett. 48 2007 6010 6013
44. K. Shen, X. Liu, Q. Li, and X. Feng Tetrahedron 64 2008 147 153
45. S. Matsukawa, I. Sekine, and A. Iitsuka Molecules 14 2009 3353 3359
46. For cyanations with acyl cyanides, see: M. Okimoto, and T. Chiba Synthesis 1996 1188 1190
47. T. Watahiki, S. Ohba, and T. Oriyama Org. Lett. 5 2003 2679 2681
48. F. Li, K. Widyan, E. Wingstrand, and C. Moberg Eur. J. Org. Chem. 2009 3917 3922
49. For cyanations with alkyl cyanoformates, see: H.M.R. Hoffmann, Z.M. Ismail, R. Hollweg, and A.R. Zein Bull. Chem. Soc. Jpn. 63 1990 1807 1810
50. D. Poirier, D. Berthiaume, and R.P. Boivin Synlett 1999 1423 1425
51. D. Berthiaume, and D. Poirier Tetrahedron 56 2000 5995 6003
52. D.R. Deardorff, C.M. Taniguchi, S.A. Tafti, H.Y. Kim, S.Y. Choi, K.J. Downey, and T.V. Nguyen J. Org. Chem. 66 2001 7191 7194
53. M. Scholl, C.-K. Lim, and G.C. Fu J. Org. Chem. 60 1995 6229 6231
54. K. Iwanami, Y. Hinakubo, and T. Oriyama Tetrahedron Lett. 46 2005 5881 5883
55. 2 (29%) and EtOH (56%).
56. 3 in MeOH to afford the corresponding cyanohydrin in 93% yield.
57. 4. After concentration, the crude material was purified by column chromatography (silica gel: 6 g, hexane-EtOAc: 6/1) to give the product 7a (115.0 mg, 96% yield) as a colorless solid.
58. Typical procedure for cyanation of ketones catalyzed by DMAP (Table 3, entry 3): To a stirred mixture of ketone 8b (0.45 mmol, 1.0 equiv.) and DMAP (5.5 mg, 0.045 mmol, 10 mol %) was added ethyl cyanoformate (3) (0.049 mL, 0.5 mol, 1.1 equiv) at room temperature under argon atmosphere. The mixture was stirred at the same temperature for 24 h. The mixture was purified by column chromatography (silica gel: 6 g, hexane-EtOAc: 4/1) to give the product 9b (88.0 mg, 99% yield) as a colorless oil.
59. Pyridine and N,N-dimethylaniline did not promote the cyanation. Therefore, the nucleophilicity of DMAP plays an important role in the cyanation, as observed in DMAP-promoted acylation of alcohols.