Stereoelectronic effects in cyclic sulfoxides, sulfones, and sulfilimines: Application of the perlin effect to conformational analysis

Chemistry - A European Journal

Volumn 13, Issue 15, 2007, Pages 4273-4281

  Wedel, Tobias ^a   Müller, Monika ^a   Podlech, Joachim ^a   Goesmann, Helmut ^a   Feldmann, Claus ^a  

^a UNIVERSITY OF KARLSRUHE   (Germany)

Author keywords

C H coupling constants; Heterocycles; Hyperconjugation; NMR spectroscopy; Perlin effect; Sulfur

Indexed keywords

CONFORMATIONS; DERIVATIVES; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY;

C-H COUPLING CONSTANTS; HETEROCYCLES; PERLIN EFFECT;

SULFUR COMPOUNDS;

EID: 34250354295     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200601468     Document Type: Article

References (57)

1. a) M. Karplus, J. Chem. Phys. 1959, 30, 11-15;
2. b) M. Karplus, J. Am. Chem. Soc. 1963, 85, 2870-2871.
3. E. Kleinpeter, A. Koch, K. Pihlaja, Tetrahedron 2005, 61, 7349-7358.
4. A. S. Perlin, B. Casu, Tetrahedron Lett. 1969, 10, 2921-2924.
5. E. Juaristi, G. Cuevas, Tetrahedron 1992, 48, 5019-5087.
6. J. D. Roberts, R. L. Webb, E. A. McElhill, J. Am. Chem. Soc. 1950, 72, 408-411.
7. C-H delocalization: G. Cuevas, K. Martinez-Mayorga, M. d. C. Fernández- Alonso, J. Jiménez-Barbero, C. L. Perrin, E. Juaristi, N. López-Mora, Angew. Chem. 2005, 117, 2412-2416;
8. Angew. Chem. Int. Ed. 2005, 44, 2360-2364.
9. S. Wolfe, B. M. Pinto, V. Varma, R. Y. N. Leung, Can. J. Chem. 1990, 68, 1051-1062.
10. a) S. David in Anomeric Effect: Origin and Consequences (Eds.; W. A. Szarek, D. Horton). American Chemical Society Symposium Series, Washington, DC, 1979;
11. b) E. Juaristi, G. Cuevas, The Anomeric Effect, CRC, Boca Raton, 1992;
12. c) E. Juaristi, M. Ordoñez in Organosulfur Chemistry - Synthetic and Stereochemical Aspects, Vol. 2 (Ed.: P. Page), Academic Press, San Diego, 1998, pp. 63-95.
13. J. E. Anderson, A. J. Bloodworth, J. Cai, A. G. Davies, N. A. Tallant, J. Chem. Soc. Chem. Commun. 1992, 1689-1691.
14. I. V. Alabugin, J. Org. Chem. 2000, 65, 3910-3919.
15. a) G. Cuevas, E. Juaristi, A. Vela, J. Phys. Chem. A 1999, 103, 932-937;
16. b) E. Juaristi, G. Cuevas, A. Vela, J. Am. Chem. Soc. 1994, 116, 5796-5804.
17. S. Wolfe, C.-K. Kim, Can. J. Chem. 1991, 69, 1408-1412.
18. a) A. S. Cieplak, J. Am. Chem. Soc. 1981, 103, 4540-4552;
19. b) A. S. Cieplak, B. D. Tait, C. R. Johnson, J. Am. Chem. Soc. 1989, 111, 8447-8462.
20. a) W. F. Bailey, A. D. Rivera, K. Rossi, Tetrahedron Lett. 1988, 29, 5621-5624;
21. b) E. Juaristi, G. Cuevas, Tetrahedron Lett. 1992, 33, 1847-1850;
22. c) E. Juaristi, G. Cuevas, A. Flores-Vela, Tetrahedron Lett. 1992, 33, 6927-6930.
23. The sulfur lone pairs and especially a sulfoxide lone pair are hardly effective as donors: a) E. Juaristi, M. Ordoñez, Tetrahedron 1994, 50, 4937-4948;
24. b) V. K. Aggarwal, J. M. Worrall, H. Adams, R. Alexander, B. F. Taylor, J. Chem. Soc. Perkin Trans. 1 1997, 21-24.
25. Participation of sulfur d orbitals has been considered repeatedly but was found to have minor influence on stereoelectronic effects: a) A. E. Reed, P. von R. Schleyer, J. Am. Chem. Soc. 1990, 112, 1434-1445;
26. b) N. D. Epiotis, R. L. Yates, F. Bernardi, S. Wolfe, J. Am. Chem. Soc. 1976, 98, 5435-5439.
27. B. A. Shainyan, I. A. Ushakov, E. N. Suslova, J. Sulfur Chem. 2006, 27, 3-13.
28. R. Notario, M. V. Roux, G. Cuevas, J. Cardenas, V. Leyva, E. Juaristi, J. Phys. Chem. A 2006, 110, 7703-7712.
29. B. A. Shainyan, S. V. Kirpichenko, Russ, J. Gen. Chem. 2003, 73, 1709-1714;
30. B. A. Shainyan, S. V. Kirpichenko, Zh. Obshch. Khim. 2003, 73, 1806-1811.
31. A sulfoxide S=O group is not properly described by an S=O double bond. This picture is used herein anyway, a) D. B. Chesnut, L. D. Quin, J. Comput. Chem. 2004, 26, 734-738;
32. b) V. M. Bzhezovskii, N. N. Il'chenko, M. B. Chura, L. G. Gorb, L. M. Yagupol'skii, Russ. J. Gen. Chem. 2005, 75, 86-93;
33. V. M. Bzhezovskii, N. N. Il'chenko, Zh. Obshch. Khim. 2005, 75, 96-104.
34. a) S. Wolfe, A. Stolow, L. A. LaJohn. Tetrahedron Lett. 1983, 24, 4071-4074;
35. b) S. Wolfe in Organic Sulfur Chemistry-Theoretical and Experimental Advances (Eds.: F. Bernardi, I. G. Csizmadia, A. Mangini), Elsevier, Amsterdam, 1985, pp. 133-190.
36. The nature of the S=N double bond has been studied: a) S. Tsuchiya, S. Mitomo, M. Seno, H. Miyamae, J. Org. Chem. 1984, 49, 3556-3559;
37. b) P. S. Kumar, P. Singh, P. Uppal, P. V. Bharatam, Bull. Chem. Soc. Jpn. 2005, 78, 1417-1424.
38. a) T. Wedel, J. Podlech, Org. Lett. 2005, 7, 4013-4015;
39. b) T. Wedel, J. Podlech, Synlett 2006, 2043-2046.
40. a) L. Müller, J. Am. Chem. Soc. 1979, 101, 4481-4484;
41. b) A. Bax. R. H. Griffey, B. L. Hawkins, J. Magn. Reson. Ser. A 1983, 55, 301-315.
42. S. Berger, S. Braun, 200 and More NMR Experiments: A Practical Course, Wiley-VCH, Weinheim, 2004.
43. Spectra and coupling constants are given in the Supporting Information.
44. G. Bodenhausen, D. J. Ruben, Chem. Phys. Lett. 1980, 69, 185-189.
45. J. Cai, A. G. Davies, C. H. Schiesser, J. Chem. Soc. Perkin Trans. 2 1994, 1151-1156.
46. I. V. Alabugin, M. Manoharan, T. A. Zeidan, J. Am. Chem. Soc. 2003, 125, 14014-14031.
47. An explanation of this term is given in footnote 33 of reference [29]; Plough is another name for the star constellation Ursa Major, also known as the big dipper.
48. W. L. Xu, Y. Z. Li, Q. S. Zhang, H. S. Zhu, Synthesis 2004, 227-232.
49. Details on the crystallographic analysis of sulfilimine 9 are given in the Supporting Information. CCDC-622411 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/ data_request/ci f.
50. a) H. Duddeck, U. Korek, D. Rosenbaum, J. Drabowicz, Magn. Reson. Chem. 1986, 24, 792-797;
51. b) H. Duddeck, Top. Stereochem. 1986, 16, 219-324.
52. a) I. Jalsovszky, F. Ruff, M. Kajtár-Peredy, I. Kövesdi. Á. Kucsman, Tetrahedron 1986, 42, 5649-5656;
53. b) I. Jalsovszky, Á. Kucsman, F. Ruff, T. Koritsánszky, G. Argay, A. Kálmán, J. Mol. Struct. 1987, 156, 165-192.
54. S. Bien, S. K. Celebi, M. Kapon, J. Chem. Soc. Perkin Trans. 2 1990, 1987-1990.
55. A. J. Kirby, The Anomeric Effect and Related Stereoelectronic Effects at Oxygen, Springer, Berlin, 1983.
56. Prepared in accordance with published procedures: a) T. Okuyama, W. Fujiwara, T. Fueno, Bull. Chem. Soc. Jpn. 1986, 59, 453-456;
57. b) V. K. Aggarwal, R. M. Steele, Ritmaleni, J. K. Barrell, I. Grayson, J. Org. Chem. 2003, 68, 4087-4090.