On the planarity of amide nitrogen. Intrinsic pyramidal nitrogen of N-acyl-7-azabicyclo[2.2.1]heptanes

Tetrahedron Letters

Volumn 39, Issue 8, 1998, Pages 865-868

  Ohwada, Tomohiko ^a   Achiwa, Takuji ^a   Okamoto, Iwao ^a   Shudo, Koichi ^a   Yamaguchi, Kentaro ^b  

^a UNIVERSITY OF TOKYO   (Japan)

^b CHIBA UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

AMIDE; HEPTANE; N ACYL 7 AZABICYCLO(2.2.1)HEPTANE; NITROGEN; UNCLASSIFIED DRUG;

ARTICLE; CHEMISTRY; CONTROLLED STUDY; CRYSTAL; DRUG STRUCTURE; NONHUMAN; TORSION;

EID: 0032546068     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)10751-1     Document Type: Article

References (34)

1. 1) a) Epstain, C. J.; Goldberger, R. F.; Anfinsen, C. B. Cold Spring Habor Symp. Quant. Biol., 1963, 28, 439.
2. b) Pauling, L. The Nature of the Chemical Bond, Cornell University Press; Cornell, 1960.
3. c)Wiberg, K. B.; Laidig, K. E. J. Am. Chem. Soc., 1987, 109, 5935-5943.
4. d)Wiberg, K. B.;Breneman, C. M. J. Am. Chem. Soc., 1992, 114, 831-840.
5. e)Laidig. K. E.; Cameron, L. M.; J. Am. Chem. Soc., 1996, 118, 1737-1742.
6. f) Fischer, G., Angew. Chem. Int., Ed. Engl., 1994, 33, 1415-1436.
7. 2) a)Stewart, W. E.; Siddall, III, T. H. Chem. Rev., 1970, 70, 517-551.
8. b)Itai, A.; Toriumi, Y.; Saito, S.; Kagechika, H.; Shudo, K. J. Am. Chem. Soc., 1992, 114, 10649-10650.
9. c) Luque, F. J.; Orozco, M. J. Chem. Soc., Perkin Trans 2, 1993, 683-691.
10. 3) a) Anet, F. A. L.; Osyany, J. M. J. Am. Chem. Soc., 1967, 89, 352-356.
11. b) Boggs, G. R.; Gerig, J. T. J. Org. Chem., 1969, 34, 1484-1487.
12. c) Review: Rauk, A.; Allen, L. C.; Mislow, K. Angew. Chem. Int., Ed. Engl., 1970, 9, 400-414.
13. d) Korn, A.; Rudolph-Bohner, S.; Moroder, L. Tetrahedron 1994, 50, 1717-1730.
14. 4) a)Winkler, F. K.; Dunitz, J. D. J. Mol. Biol., 1971, 59, 169-182.
15. b) Dunitz, J. D.; Winkler, F. K., Acta. Cryst. 1975. B31, 251-263.
16. 5) (a) Somayaji, V.; Brown, R. S. J. Org. Chem., 1986, 51, 2676-2686.
17. (b) Wang, Q.-P.; Bennet, A. J.; Brown, R. S.; Santariero, B. D. J. Am. Chem. Soc., 1991, 113, 5757-5765.
18. (c) Greenberg, A.; Moore, D. T.; DuBois, T. D. J. Am. Chem. Soc., 1996, 118, 8658-8668.
19. 6) (a) Yamada, S. Angew. Chem. Int. Ed. Engl., 1993, 32, 1083-1085.
20. (b) Yamada, S. J. Org. Chem., 1996, 61, 941-946,
21. (c) Yamada, S.; Sugaki, T.; Matsuzaki, K., J. Org. Chem., 1996, 61, 5932-5938.
22. 22)| as defined in references 4b and 6a (see footnote 4c).
23. 7) (a) Shao, H.; Jiang, X.; Gantzel, P.; Goodman, M. Chemistry & Biology, 1994, 1, 231-234.
24. (b) Goodman, M.; Shao, H. Pure & Appl. Chem., 1996, 68, 1303-1308.
25. (c) Wipf, P.; Fritch, P. C. J. Org. Chem., 1994, 59, 4875-4886.
26. 8) a) Chen, Z.; Trudell, M. L., Chem. Rev., 1996, 96, 1179-1193.
27. b) Szántay, C.; Kardos-Balogh, Z.; Szántay, C., Jr. The Alkaloids, Chemistry and Pharmacology, 1995, Vol 46, chapter 3, 95-125, Ed. by Cordell 1, G. A., Academic Press, San Diego, U.S.A..
28. 1)=!.54050 Å, T=296 K, R=0.048 for 1635 unique reflections. Further details of the crystallographic data will be discussed in a full paper.
29. 10) Yamaguchi, K. Chem. Pharm. Bull., 1993, 41, 424-429.
30. 11) The out-of-piane angle (α) defined here is exactly twice the magnitude of the tilt angle of an amide bond as defined in reference 5.
31. 12) Drew, M. G. B.: George, A. V.; Isaacs, N. S.; Rzepa, H. S. J. Chem. Soc., Perkin Trans. 1, 1985, 1277-1284.
32. 13) Fletcher, S.R.; Baker, R.; Chambers, M.S.; Herbert, R.H.; Hobbs, S.C; Thomas, S.R.; Verrier, H.M.; Watt, A.P.; Ball, R.G. J. Org. Chem., 1994, 59, 1771-1778.
33. 14) Adam, W.; Grabowski, S.; Hinz, R.F.; Lucchini, V.; Peters, E. M.; Peters, K.; Rebollo, H.; Schnering, H.G. von., Chem. Ber., 1987, 120, 2075-2079.
34. 15) The 126 examples of N-benzoyl secondary amines include 20 cases of pyramidalized nitrogen amides (θ: 339.9 ° (mean)), of which most are N-benzoy) aziridines (4 cases) and N-benzoyl cyclic amides bearing an adjacent bulky tert-butyl group (11 cases) (see reference 6). The mean value (θ) of the remaining 106 examples is 358.9 °. The 126 examples include only amide compounds among N-benzoyl secondary amines (150 cases), that is, excluding ureas and urethanes. The mean values of the summation of the three valence angles around the nitrogen (θ) and the N-C(O) bonds for all examples of N-benzoyl secondary amines (including ureas and urethanes, 150 cases) in the Cambridge Structural Database are 355.6(8) ° and 1.382(3) Å, respectively. The 35 examples include N-(substituted benzoyl)pyrrolidines and 3-pyrrolines and S, excluding pyrroles. The mean values of the summation of the three valence angles around the nitrogen (θ) and the N-C(O) bonds for 34 examples of N-(substituted benzoyl)pyrrolidines and 3-pyrrolines (excluding 5 from the 35 examples) in the Cambridge Structural Database are 357.4(7)° and 1.345(2) Å, respectively.