Double insertion of isocyanides into dihydropyridines: Direct access to substituted benzimidazolium salts

Angewandte Chemie - International Edition

Volumn 46, Issue 17, 2007, Pages 3043-3046

  Masdeu, Carme ^a   Gómez, Elena ^a   Williams, Nana Aba O ^a   Lavilla, Rodolfo ^a,b  

^a INSTITUTE FOR RESEARCH IN BIOMEDICINE   (Spain)

^b UNIVERSITY OF BARCELONA   (Spain)

Author keywords

Cascade reactions; Heterocycles; Insertion; Isocyanides; Synthetic methods

Indexed keywords

CHEMICAL BONDS; DERIVATIVES; MOLECULAR STRUCTURE; PYRIDINE; SALTS; SUBSTITUTION REACTIONS;

BENZIMIDAZOLE CORE; CASCADE REACTIONS; DIHYDROPYRIDINES; HETEROCYCLES; SYNTHETIC METHODS;

CYANIDES;

BENZIMIDAZOLE DERIVATIVE; CYANIDE; DIHYDROPYRIDINE DERIVATIVE;

ARTICLE; CHEMICAL STRUCTURE; CHEMISTRY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; SYNTHESIS;

BENZIMIDAZOLES; CYANIDES; DIHYDROPYRIDINES; MAGNETIC RESONANCE SPECTROSCOPY; MOLECULAR STRUCTURE;

EID: 34250831544     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200605070     Document Type: Article

References (44)

1. a) A. Dömling, Chem. Rev. 2006, 106, 17-89;
2. b) A. Dömling, I. Ugi, Angew. Chem. 2000, 112, 3300-3344;
3. Angew. Chem. Int. Ed. 2000, 39, 3168-3210.
4. For an overview of MCRs, see: Multicomponent Reactions (Eds.: J. Zhu, H. Bienaymé), Wiley-VCH, Weinheim, 2005.
5. For recent results, see: a) J. L. Díaz, M. Miguel, R. Lavilla, J. Org. Chem. 2004, 69, 3550-3553;
6. b) O. Jiménez, G. de la Rosa, R. Lavilla, Angew. Chem. 2005, 117, 6679-6683;
7. Angew. Chem. Int. Ed. 2005, 44, 6521-6525;
8. c) N. A. O. Williams, C. Masdeu, J. L. Díaz, R. Lavilla, Org. Lett. 2006, 8, 5789-5792.
9. C. Masdeu, E. Gómez, N. A. Williams, R. Lavilla, QSAR Comb. Sci. 2006, 25, 465-473.
10. In fact, in the bromine-promoted reaction, salt 4a (in the bromide form) was detected as a by-product (< 1 %).
11. For a recent review on the chemistry of DHPs, see: R. Lavilla, J. Chem. Soc. Perkin Trans. 1 2002, 1141-1156.
12. For reviews on the chemistry and synthesis of benzimidazoles and derivatives, see: a) M. R. Grimmett in Science of Synthesis, Vol. 12, Thieme, Stuttgart, 2002, chap. 12.4;
13. b) M. R. Grimmett in Comprehensive Heterocyclic Chemistry II, Vol. 3 (Eds.: A. R. Katritzky, C. W. Rees, E. F. V. Scriven), Pergamon, Oxford, 1996, chap. 3.02.
14. For recent reviews, see: a) W. A. Herrmann, Angew. Chem. 2002, 114, 1342-1363;
15. Angew. Chem. Int. Ed. 2002, 41, 1290-1309;
16. b) V. Nair, S. Bindu, V. Sreekumar, Angew. Chem. 2004, 116, 5240-5245;
17. Angew. Chem. Int. Ed. 2004, 43, 5130-5135;
18. c) G. A. Grasa, R. Singh, S. P. Nolan, Synthesis 2004, 971-985.
19. a) W.-G. Huang, S.-M. Zhang, L.-Y. Dai, Y.-K. Shan, J. Chem. Res. 2004, 506-507;
20. for applications in materials science, see: b) T. Akutagawa, T. Hasegawa, T. Nakamura, T. Inabe, G. Saito, Chem. Eur. J. 2002, 8, 4402-4411.
21. a) Y.-F. Li, G.-F. Wang, P.-L. He, W.-G. Huang, F.-H. Zhu, H.-Y. Gao, W. Tang, Y. Luo, C.-L. Feng, L.-P. Shi, Y.-D. Ren, W. Lu, J.-P. Zuo, J. Med. Chem. 2006, 49, 4790-4794;
22. b) J. Howarth, K. Hanlon, Bioorg. Med. Chem. Lett. 2003, 13, 2017-2020;
23. c) J. Pastor, J. G. Siro, J. L. García-Navío, J. J. Vaquero, J. Alvarez-Builla, F. Gago, B. de Pascual-Teresa, M. Pastor, M. M. Rodrigo, J. Org. Chem. 1997, 62, 5476-5483.
24. 13C-labeled ethyl formate, by following the reported procedure: H. Deng, J. F. Schindler, K. B. Berst, B. V. Plapp, R. Callender, Biochemistry 1998, 37, 14 267-14 278.
25. 3 solutions of 4a.
26. M. E. Brewster, J. J. Kaminski, Z. Gabanyi, K. Czako, A. Simay, N. Bodor, Tetrahedron 1989, 45, 4395-4402.
27. For a review, see: a) H. Togo, S. Iida, Synlett 2006, 2159-2175;
28. for the coexistence of iodine-based oxidants with isocyanides, see: b) T. Ngouansavanh, J. Zhu, Angew. Chem. 2006, 118, 3575-3577;
29. Angew. Chem. Int. Ed. 2006, 45, 3495-3497.
30. a) R. Lavilla, R. Kumar, O. Coll, C. Masdeu, A. Spada, J. Bosch, E. Espinosa, E. Molins, Chem. Eur. J. 2000, 6, 1763-1772;
31. b) R. Lavilla, Curr. Org. Chem. 2004, 8, 715-737.
32. The double incorporation of isocyanides at electrophilic centers has been documented: a) H. J. Kabbe, Chem. Ber. 1969, 102, 1404-1409;
33. b) G. Bez, C.-G. Zao, Org. Lett. 2003, 5, 4991-4993;
34. c) M. Oshita, K. Yamashita, M. Tobisu, N. Chatani, J. Am. Chem. Soc. 2005, 127, 761-766;
35. d) V. S. Korotkov, O. V. Larionov, A. de Meijere, Synthesis 2006, 3542-3546.
36. For the interaction of C-acylnitrilium ions with π systems, see: T. Livinghouse, Tetrahedron 1999, 55, 9947-9978.
37. For a recent review, see: K. C. Nicolaou, D. J. Edmonds, P. G. Bulger, Angew. Chem. 2006, 118, 7292-7344;
38. Angew. Chem. Int. Ed. 2006, 45, 7134-7186.
39. For instance, see: a) A. M. van Leusen, J. Wildeman, O. H. Oldenziel, J. Org. Chem. 1977, 42, 1153-1159;
40. b) H. Bienaymé, K. Bouzid, Angew. Chem. 1998, 110, 2349-2352;
41. Angew. Chem. Int. Ed. 1998, 37, 2234-2237;
42. c) J.-C. Berthet, M. Nierlich, M. Ephritikhine, Eur. J. Org. Chem. 2002, 375-378.
43. A β-carboxamido-1,4-DHP is oxidized to the pyridinium salt over 20 times faster than the corresponding β-methoxycarbonyl analogue. Cyano- and acetyl-DHPs are oxidized at slower rates. See: M. E. Brewster, A. Simay, K. Czako, D. Winwood, H. Farag, N. Bodor, J. Org. Chem. 1989, 54, 3721-3726.
44. 2 and an equimolar mixture of cyclohexyl and benzyl isocyanides, the heteroadducts incorporating one cyclohexyl and one benzyl residue were detected (HPLC-MS) together with the corresponding homoadducts 4a and 4k.