Hydrolysis and hydrogenolysis of formamidines: N,N-dimethyl and N,N- dibenzyl formamidines as protective groups for primary amines

Journal of Organic Chemistry

Volumn 64, Issue 3, 1999, Pages 991-997

  Vincent, Stéphane ^a   Mioskowski, Charles ^a   Lebeau, Luc ^a  

^a UNIVERSITÉ DE STRASBOURG   (France)

Author keywords

[No Author keywords available]

Indexed keywords

AMINE; FORMAMIDINE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; HYDROLYSIS; MOLECULAR DYNAMICS; REACTION ANALYSIS; SYNTHESIS;

EID: 0033525164     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo980099g     Document Type: Article

References (40)

1. Greene, T. W.; Wuts, P. G. M. Protective group in organic synthesis, 2nd ed.; Wiley: New York, 1991.
2. Zemlicka, J. Collect. Czech. Chem. Commun. 1963, 28, 1060-1062.
3. Beaucage, S. L.; Iyer, R. P. Tetrahedron 1992, 48, 2223-2311.
4. Seela, F.; Mertens, R.; Kazimierczuk, Z. Helv. Chim. Acta 1992, 75, 2298-2306.
5. Theisen, P.; McCollum, C.; Andrus, A. Nucleosides Nucleotides 1993, 12, 1033-1046.
6. Arnold, L.; Tocik, Z.; Bradkova, E.; Hostomsky, Z.; Paces, V.; Smrt, J. Collect. Czech. Chem. Commun. 1989, 54, 523-532.
7. Arnold, L.; Smrt, J.; Zajicek, J.; Ott, G.; Schiesswohl, M.; Sprinzl, M. Collect. Czech. Chem. Commun. 1991, 56, 1948-1956.
8. Vu, H.; McCollum, C.; Jacobson, K.; Theisen, P.; Vinayak, R.; Spiess, E.; Andrus, A. Tetrahedron Lett. 1990, 31, 7269-7272.
9. McBride, L. J.; Kierzek, R.; Beaucage, S. L.; Caruthers, M. H. J. Am. Chem. Soc. 1986, 108, 2040-2048.
10. Froehler, B. C.; Matteuci, M. D. Nucleic Acids Res. 1983, 11, 8031-8036.
11. Holy, A.; Zemlicka, J. Collect. Czech. Chem. Commun. 1968, 34, 2449-2459.
12. Zemlicka, J.; Chladek, S.; Holy, A.; Smrt, J. Collect. Czech. Chem. Commun. 1966, 31, 3198-3211.
13. Vincent, S.; Mons, S.; Lebeau, L.; Mioskowski, C. Tetrahedron Lett. 1997, 38, 7527-7530.
14. Möhrle, H.; Engelsing, R. Arch. Pharmaz. 1972, 306, 325-338.
15. Granik, V. G. Russ. Chem. Rev. 1983, 52, 377-393.
16. Boyd, G. V. In The chemistry of amidines and imidates; Patai, S., Rappoport, Z., Eds.; John Wiley & Sons: Chichester, 1991; Vol. 2, pp 339-366.
17. Abdulla, R. F.; Brinkmeyer, R. S. Tetrahedron 1979, 35, 1675-1735.
18. Meerwein, H.; Florian, W.; Schön, N.; Stopp, G. Liebigs Ann. Chem. 1961, 641, 1-39.
19. Brederek, H.; Simchen, G.; Rebsdat, S.; Kantlehner, W.; Horn, P.; Wahl, R.; Hoffmann, H.; Grieshaber, P. Chem. Ber. 1968, 101, 41-50.
20. Patai, S. In The chemistry of functional groups: The chemistry of amidines and imidates; Patai, S., Ed.; Wiley: London, 1975; Vol. 1.
21. Fernandez, B.; Perillo, I.; Lamdan, S. J. Chem. Soc., Perkin Trans. 2 1973, 1371-1374.
22. Perillo, I.; Fernandez, B.; Lamdan, S. J. Chem. Soc., Perkin Trans. 2 1977, 2068-2072.
23. Halliday, J. D.; Symons, E. A. Can. J. Chem. 1978, 56, 1463-1469.
24. Perrin, C. L.; Arrhenius, G. M. L. J. Am. Chem. Soc. 1982, 104, 2839-2842.
25. Interestingly, it was recently reported that hydrolysis of dimethyl formamidines in absolute ethanol in the presence of 2 equiv of zinc chloride required 24 h at room temperature to quantitatively afford the corresponding N-alkyl formamide: Toste, D.; McNulty, J.; Still, I. W. J. Synth. Commun. 1994, 24, 1617-1624.
26. Christensen, J. J.; Izatt, R. M.; Wrathall, D. P.; Hansen, L. D. J. Chem. Soc. A 1969, 1212-1223.
27. Smith, J. A.; Taylor, H. J. Chem. Soc. B 1969, 66-67.
28. Because of steric hindrance, 2,6-dimethylaniline derivatives were very resistant to hydrolysis (Table 1, entries 11-13).
29. In the hydrolysis of N-aryl N′,N′-disubstituted formamidines under basic conditions, the intermediate species 3b (Scheme 1) is presumably not fully protonated at N′.
30. DeWolfe, R. H.; Newcomb, R. C. J. Org. Chem. 1971, 36, 3870-3878.
31. Cunningham, I. D. J. Chem. Soc., Perkin Trans. 2 1988, 1485-1490.
32. Breshears, S. R.; Wang, S. S.; Bechtolt, S. G.; Christensen, B. E. J. Am. Chem. Soc. 1959, 81, 3789-3792.
33. Jones, R. C. F.; Turner, I.; Howard, K. J. Tetrahedron Lett. 1993, 34, 6329-6332.
34. Jones, R. C. F.; Hirst, S. C. Tetrahedron Lett. 1989, 30, 5365-5368.
35. Mailhe, M. A. C. R. Hebd. Scéances Acad. Sci. 1923, 176, 1159-1161.
36. Losse, G.; Nadolski, D. J. Prakt. Chem. 1964, 24, 118-124.
37. Abrams, W. R.; Kallen, R. G. J. Am. Chem. Soc. 1976, 98, 7777-7789.
38. Lebeau, L.; Oudet, P.; Mioskowski, C. Helv. Chim. Acta 1991, 74, 1697-1706.
39. Hindered primary amines required prolonged reaction time at higher temperature (50-60°C).
40. The reaction can be run in anhydrous DMF with a comparable yield and without any formation of N, N-dimethyl formamidine.