Acid-mediated amine exchange of N,N-dimethylformamidines: Preparation of electron-rich formamidines

Synlett

Volumn , Issue 14, 2005, Pages 2214-2218

  Díaz, David D ^a   Lewis, Warren G ^a   Finn, M G ^a  

^a SCRIPPS RESEARCH INSTITUTE   (United States)

Author keywords

Acid; Amine exchange; Formamidine; Imidazole

Indexed keywords

ACID; AMINE; FORMAMIDINE; IMIDAZOLE DERIVATIVE; N,N DIMETHYLFORMAMIDINE; PROPARGYLAMINE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; ELECTRON TRANSPORT; REACTION ANALYSIS; SYNTHESIS;

EID: 24744441692     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2005-872249     Document Type: Article

References (45)

1. (a) Ziegleskylakakis, K.; Nill, S.; Pan, J. F.; Andrae, U. Environ. Mol. Mutagen. 1998, 31, 362.
2. (b) Leung, V. K. S. Chan, T. Y. K.; Yeung, V. T. F. J. Toxicol., Clin. Toxicol. 1999, 37, 513.
3. (c) Goto, T.; Sakashita, H.; Murakami, K.; Sugiura, M.; Kondo, T.; Fukaya, C. Chem. Pharm. Bull. 1997, 45, 305.
4. (a) Böhme, F.; Kunert, C.; Klinger, C.; Komber, H. Macromol. Symp. 1998, 128, 183.
5. (b) Böhme, F.; Klinger, C.; Komber, H.; Haussler, L.; Jehnichen, D. J. Polym. Sci., Part A: Polym. Chem. 1998, 36, 929.
6. (c) Wulff, G.; Schönfeld, R. Adv. Mater. 1998, 10, 957.
7. (d) Marchildon, L.; Daneault, C.; Leduc, C.; Sain, M. M. Cellulose Chem. Technol. 1996, 30, 473.
8. (e) Rillich, M.; Haussler, L.; Jehnichen, D.; Böhme, F. Polym. Bull. 1995, 34, 43.
9. (f) Meier, J. Papier 1994, 48, 677.
10. Taylor, E. C.; Ehrhart, W. A. J. Org. Chem. 1963, 28, 1108.
11. For a synthesis of unsymmetrically substituted formamidinium salts using orthoformates and acetic acid, see: Wicherink, S. C.; Scheeren, J. W.; Nivard, R. J. F. Synthesis 1977, 273.
12. (a) The Chemistry of Amidines and Imidates, Vol. 2; Patai, S.; Rappoport, Z., Eds.; J. Wiley and Sons: New York, 1991.
13. (b) Granik, V. G. Russ. Chem. Rev. 1983, 52, 377.
14. (a) Ripka, A. S.; Díaz, D. D.; Sharpless, K. B.; Finn, M. G. Org. Lett. 2003, 5, 1531.
15. (b) Díaz, D. D.; Finn, M. G. Chem.-Eur. J. 2004, 10, 303.
16. (c) Díaz, D. D.; Finn, M. G. Org. Lett. 2004, 6, 43.
17. (d) Díaz, D. D.; Finn, M. G. Chem. Commun. 2004, 2514.
18. See ref. 6d and ref. 3-6 cited therein.
19. For examples using non-protic solvents such as toluene, particularly with secondary amines, see: (a) Meyers, A. I.; Edwards, P. D.; Rieker, W. F.; Bailey, T. R. J. Am. Chem. Soc. 1984, 106, 3270.
20. (b) Beeley, L. J.; Rockell, J. M. Tetrahedron Lett. 1990, 31, 417.
21. (c) Meyers, A. I.; Millar, D. B.; White, F. H. J. Am. Chem. Soc. 1988, 110, 4778.
22. (a) Harnden, M. R.; Parkin, A.; Wyatt, P. G. Tetrahedron Lett. 1988, 29, 701.
23. (b) Harnden, M. R.; Jarvest, R. L. J. Chem. Soc., Perkin Trans. 1 1989, 2207.
24. (c) Harnden, M. R.; Jennings, L. J.; McKie, C. M. D.; Parkin, A. Synthesis 1990, 893.
25. Eilingsfeld, H. Chem. Ber. 1965, 98, 1308.
26. (a) Katritzky, A. R.; Huang, T.-B.; Voronkov, M. V. J. Org. Chem. 2000, 65, 2246.
27. (b) Guillot, N.; Viehe, H. G.; Tinant, B.; Declercq, J. P. Tetrahedron 1990, 46, 3897.
28. (c) Jones, S. D.; Kennewell, P. D.; Tulley, W. R.; Westwood, R. J. Chem. Soc., Perkin Trans. 1 1990, 447.
29. (d) Maquestiau, A.; Eynde, J.-J. V. Tetrahedron 1987, 43, 4195.
30. (e) Bátori, S.; Sándor, P.; Messmer, A. Heterocycles 1990, 31, 289.
31. (a) Shallop, A. J.; Gaffney, B. L.; Jones, R. A. J. Org. Chem. 2003, 68, 8657.
32. (b) Alarcon, K.; Martelli, A.; Demeunynck, M.; Lhomme, J. Tetrahedron Lett. 2000, 41, 7211.
33. (c) Sternfeld, F.; Guiblin, A. R.; Jelley, R. A.; Matassa, V. G.; Reeve, A. J.; Hunt, P. A.; Beer, M. S.; Heald, A.; Stanton, J. A.; Sohal, B.; Watt, P. A.; Street, L. J. J. Med. Chem. 1999, 42, 677.
34. (d) Zelenin, K. N.; Khrustalev, V. A.; Sergutina, V. P. Zh. Org. Khim. 1980, 16, 276.
35. (e) Khrustalev, V. A.; Zelenin, K. N.; Sergutina, V. P. Zh. Org. Khim. 1979, 15, 2288; and ref. 2 cited therein.
36. Stocks, M. J.; Cheshire, D. R.; Reynolds, R. Org. Lett. 2004, 6, 2969.
37. All the starting N,N-dimethylformamidines were synthesized by the usual methods reported previously in the literature, see: (a) Abdulla, R. F.; Brinkmeyer, R. S. Tetrahedron 1979, 33, 1675.
38. (b) ref. 11a.
39. For studies concerning the site of protonation of N,N- dimethylformamidines, see: Raczynska, E. D.; Maria, P.-C.; Gal, J.-F.; Decouzon, M. J. Org. Chem. 1992, 57, 5730; and references therein.
40. (a) N,N′-Dipropargylformamidine is mentioned in passing in: Dötz, K. H.; Kroll, F.; Harms, K. J. Organomet. Chem. 1993, 459, 169.
41. (b) We find that at least some cyclization to the corresponding imidazole cannot be prevented when the synthesis of the formamidine is attempted either from orthoformate or from propargyldimethylformamidine at elevated temperatures; at r.t. the required exchange reaction is prohibitively slow.
42. (a) Jezewski, A.; Jurczak, J.; Lidert, Z.; Tice, C. M. J. Heterocycl. Chem. 2001, 38, 645.
43. (b) Taylor, E. C.; Zhou, P. Tetrahedron Lett. 1997, 38, 4339.
44. (c) Eloy, F.; Deryckere, A.; Maffrand, J. P. Eur. J. Med. Chem. 1974, 602.
45. (d) Iwai, I.; Hiraoka, T. Chem. Pharm. Bull. 1964, 12, 813.