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Tormena, C.F.; Rittner, R.; Contreras, R.H.; Peralta, J.E. "Anomeric effect on geminal and vicinal JHH NMR coupling constants" (2004) Journal of Physical Chemistry A. 108(38):7762-7768
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Abstract:

Trends for geminal (2JHH) and vicinal ( 3JHH) nuclear magnetic resonance indirect spin-spin coupling constants, SSCCs, for 2-methylthiirane (5) and 2-methyloxirane (6) are studied both from experimental and theoretical points of view to determine the influence of hyperconjugative interactions on these couplings. These two analogous compounds were chosen because it was expected that they exhibit quite different anomeric effects. Hyperconjugative interactions are investigated using the "natural bond orbital" method. Coupling constants are calculated within the density functional theory including all four scalar contributions, that is, the Fermi contact, the spin-dipolar, and the paramagnetic and diamagnetic spin-orbital contributions. Solvent dielectric effects are taken into account using Tomasi's polarizable continuum model. Results for geminal couplings are consistent with linear correlations connecting 2J HH with the coupling pathway occupation numbers taken from the literature. The present analysis suggests that both 2JHH and 3JHH coupling constants are sensitive probes to gauge the anomeric effect, as well as other hyperconjugative interactions.

Registro:

Documento: Artículo
Título:Anomeric effect on geminal and vicinal JHH NMR coupling constants
Autor:Tormena, C.F.; Rittner, R.; Contreras, R.H.; Peralta, J.E.
Filiación:Departamento de Química, Fac. Filos. Cie./L. Ribeirao Preto, Universidade de São Paulo, Av. Bandeirantes 3900, 14040-901 Ribeirão Preto, SP, Brazil
Phys.-Organic Chemistry Laboratory, Instituto de Química, Universidade Estadual de Campinas, Caixa Postal 6154, CEP:13084-971, Campinas, S. Paulo, Brazil
Department of Physics, University of Buenos Aires, Ciudad Universitaria, Pab. 1, (1428) Buenos Aires, Argentina
Palabras clave:Chemical bonds; Diamagnetism; Dielectric properties; Molecular structure; Nuclear magnetic resonance spectroscopy; Paramagnetism; Protons; Anomeric effect; Coupling constant; Diamagnetic spin; Spin-spin coupling; Isomers
Año:2004
Volumen:108
Número:38
Página de inicio:7762
Página de fin:7768
DOI: http://dx.doi.org/10.1021/jp047226z
Título revista:Journal of Physical Chemistry A
Título revista abreviado:J Phys Chem A
ISSN:10895639
CODEN:JPCAF
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10895639_v108_n38_p7762_Tormena

Referencias:

  • Eliel, E.L., Wilen, S.H., Mander, L.N., (1994) Stereochemistry of Organic Compounds, , John Wiley & Sons: New York
  • Kirby, J.A., (2000) Stereoelectronic Effects, , Oxford University Press: New York
  • Morris, D.G., (2001) Stereochemistry, , The Royal Society of Chemistry: Exeter, U.K
  • Juaristi, E., (1995) Conformational Behavior of Six-membered Rings: Analysis, Dynamics, and Stereoelectronic Effects, , VCH Publishers: New York
  • Perrin, C.L., (2002) Acc. Chem. Res., 35, p. 28
  • Reed, A.E., Schleyer, P.V.R., (1990) J. Am. Chem. Soc., 112, p. 1434
  • King, J.F., Rathore, R., Guo, Z., Li, M., Payne, N.C., (2000) J. Am. Chem. Soc., 122, p. 10308
  • Reed, A.E., Curtis, L.A., Weinhold, F., (1988) Chem. Rev., 88, p. 899
  • Alabugin, I.V., (2000) J. Org. Chem., 65, p. 3910
  • Hetémyi, A., Martinek, T.A., Lázár, L., Zalán, Z., Fülöp, F., (2003) J. Org. Chem., 68, p. 5705
  • Alabugin, I.V., Manoharan, M., Zeidan, T.A., (2003) J. Am. Chem. Soc., 125, p. 14015
  • Perlin, A.S., Casu, B., (1969) Tetrahedron Lett., 2921
  • Wolfe, S., Pinto, B.M., Varma, V., Leung, R.Y.N., (1990) Can. J. Chem., 68, p. 1051
  • Cuevas, G., Juaristi, E., Vela, A., (1999) J. Phys. Chem. A, 103, p. 932
  • Cuevas, G., Juaristi, E., (2002) J. Am. Chem. Soc., 124, p. 13088
  • Malkina, O.L., Hricovíni, M., Bízik, F., Malkin, V.G., (2001) J. Phys. Chem. A, 105, p. 9188
  • Cloran, F., Carmichael, I., Serianni, A.S., (1999) J. Phys. Chem. A, 103, p. 3783
  • Cloran, F., Zhu, Y., Osborn, J., Carmichael, I., Serianni, A.S., (2000) J. Am. Chem. Soc., 122, p. 6435
  • Stenutz, R., Carmichael, I., Widmalm, G., Serianni, A.S., (2002) J. Org. Chem., 67, p. 949
  • Sproviero, E.M., Burton, G., (2002) J. Phys. Chem. A, 106, p. 7834
  • Ramsey, N.F., (1953) Phys. Rev., 91, p. 303
  • Contreras, R.H., Barone, V., Peralta, J.E., Facelli, J.C., (2003) Annu. Rep. NMR Spectrosc., 51, p. 167
  • Contreras, R.H., Peralta, J.E., Giribet, C.G., Ruiz De Azúa, M.C., Facelli, J.C., (2000) Annu. Rep. NMR Spectrosc., 41, p. 55
  • Mahaim, C., Currupt, P.A., Vogel, P., (1985) Helv. Chim. Acta, 68, p. 2182
  • Pople, J.A., Bothner-By, A.A., (1965) J. Chem. Phys., 42, p. 1339
  • Barfield, M., Grant, D., (1963) J. Am. Chem. Soc., 85, p. 1899
  • Wong, T.C., Clark, G.R., (1944) J. Chem. Soc., Chem. Commun., p. 1518
  • Williams, D.H., Bacca, N.S., (1965) Chem. Ind. (London), 506
  • Sternhell, S., (1969) Q. Rev., 23, p. 236
  • Contreras, R.H., Peralta, J.E., (2000) Prog. Nucl. Magn. Reson. Spectrosc., 37, p. 321
  • Freitas, M.P., Rittner, R., Tormena, C.F., Abraham, R.J., (2001) J. Phys. Org. Chem., 14, p. 317
  • Yoshinaga, F., Tormena, C.F., Freitas, M.P., Rittner, R., Abraham, R.J., (2002) J. Chem. Soc., Perkin Trans., 2, p. 1494
  • Freitas, M.P., Tormena, C.F., Rittner, R., Abraham, R.J., (2003) J. Phys. Org. Chem., 16, p. 27
  • Karplus, M., (1959) J. Chem. Phys., 30, p. 11
  • Esteban, A.L., Galache, M.P., Mora, F., Diez, E., Casanueva, J., Fabian, J.S., Barone, V., Contreras, R.H., (2001) J. Phys. Chem. A, 105, p. 5298
  • Minch, M.J., (1994) Conc. Magn. Reson., 6, p. 41
  • Thomas, W.A., (1997) Prog. NMR Spectrosc., 30, p. 183
  • Altona, C., (1996) Encyclopedia of NMR, 8, p. 4909. , Grant, D. M., Harris, R. K., Eds.; Wiley: Chichester, U.K
  • Imai, K., Osawa, E., (1990) Magn. Reson. Chem., 28, p. 668
  • Bent, H.A., (1961) Chem. Rev., 61, p. 275
  • Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Zakrzewski, V.G., Pople, J.A., (1998) Gaussian 98, Revision A., 7. , Gaussian, Inc.: Pittsburgh, PA
  • Becke, A.D., (1988) Phys. Rev., 38, p. 3098
  • Lee, C., Yang, W., Parr, R., (1988) G. Phys. Rev. B, 37, p. 785
  • Glendening, E.D., Reed, A.E., Carpenter, J.E., Weinhold, F., (1998) NBO, Version 3.1, , Gaussian, Inc.: Pittsburgh, PA, Included in the Gaussian98 package of programs
  • Pople, J.A., Beveridge, D.L., Approximate Molecular Orbital Theory, p. 1970. , McGraw-Hill: New York
  • Sychrovský, V., Gräfenstein, J., Cremer, D., (2000) J. Chem. Phys., 113, p. 3530
  • Helgaker, T., Watson, M., Handy, N.C., (2000) J. Chem. Phys., 113, p. 9402
  • Barone, V., Peralta, J.E., Contreras, R.H., Snyder, J.P., (2002) J. Phys. Chem. A, 106, p. 5607
  • Helgaker, T., Jensen, H.J.A., Jørgensen, P., Olsen, J., Ruud, K., Axclgren, H., Andersen, T., Vahtras, O., (1999) Dalton, Version 1.1, , http://www.kjemi.uio.no/software/dalton/dalton.html, University of Oslo: Oslo, Norway
  • Provasi, P.F., Aucar, G.A., Sauer, S.P.A., (2001) J. Chem. Phys., 115, p. 1981
  • Kendall, R.A., Dunning, T.H., Harrison, R.J., (1992) J. Chem. Phys., 96, p. 6796
  • Helgaker, T., Jaszuński, M., Rudd, K., (1999) Chem. Rev., 99, p. 293
  • Peralta, J.E., Scuseria, G.E., Cheeseman, J.R., Frisch, M.J., (2003) Chem. Phys. Lett., 375, p. 452
  • Mertius, S., Scrocco, E., Tomasi, J., (1981) Chem. Phys., 55, p. 117
  • Mertius, S., Tomasi, J., (1982) Chem. Phys., 65, p. 239
  • Elleman, D.D., Manatt, S.L., (1962) J. Mol. Spectrosc., 9, p. 477
  • Manatt, S.L., Elleman, D.D., Brois, S.J., (1965) J. Am. Chem. Soc., 87, p. 2220
  • Pérez, J.E., Ortíz, F.S., Contreras, R.H., Giribet, C.G., Ruiz De Azúa, M.C., (1990) J. Mol. Struct.; THEOCHEM, 210, p. 193
  • Grayson, M., Sauer, S.P.A., (2000) Mol. Phys., 98, p. 1981
  • Eliel, E.L., Giza, G.A., (1968) J. Org. Chem., 33, p. 3754
  • Lemieux, R.U., Pavia, A.A., Marti, J.C., Watanabe, K.A., (1969) Can. J. Chem., 47, p. 4427
  • Ando, I., Inoue, Y., Watanabe, S., Sakamoto, Y., Webb, G.A., (1984) J. Mol. Liq., 27, p. 179
  • Taha, A.N., True, N.S.J., (2000) Phys. Chem. A, 104, p. 2985
  • Chuck, R.J., Gilles, D.G., Randall, E.W., (1969) Mol. Phys., 16, p. 121
  • Vaara, J., Kaski, J., Jokisaari, J., Diehl, P., (1997) J. Phys. Chem. A, 101, p. 5069
  • Provasi, P.F., Aucar, G.A., Sauer, S.P.A., (2003) Int. J. Mol. Sci., 4, p. 231
  • Hansen, P.E., (1989) The Chemistry of Double-Bonded Functional Groups, , Patai, S., Ed.; Wiley: New York, chapter 3
  • Barone, V., Peralta, J.E., Contreras, R.H., (2001) J. Comput. Chem., 22, p. 1615
  • Gil, M.S., Von Philipsborn, W., (1989) Magn. Reson. Chem., 27, p. 409
  • Hansen, M.J., Wendt, M.A., Weinhold, F., Farrar, T.C., (2002) Mol. Phys., 100, p. 2807
  • Hu, S.-J., Bax, A., (1997) J. Am. Chem. Soc., 119, p. 6360

Citas:

---------- APA ----------
Tormena, C.F., Rittner, R., Contreras, R.H. & Peralta, J.E. (2004) . Anomeric effect on geminal and vicinal JHH NMR coupling constants. Journal of Physical Chemistry A, 108(38), 7762-7768.
http://dx.doi.org/10.1021/jp047226z
---------- CHICAGO ----------
Tormena, C.F., Rittner, R., Contreras, R.H., Peralta, J.E. "Anomeric effect on geminal and vicinal JHH NMR coupling constants" . Journal of Physical Chemistry A 108, no. 38 (2004) : 7762-7768.
http://dx.doi.org/10.1021/jp047226z
---------- MLA ----------
Tormena, C.F., Rittner, R., Contreras, R.H., Peralta, J.E. "Anomeric effect on geminal and vicinal JHH NMR coupling constants" . Journal of Physical Chemistry A, vol. 108, no. 38, 2004, pp. 7762-7768.
http://dx.doi.org/10.1021/jp047226z
---------- VANCOUVER ----------
Tormena, C.F., Rittner, R., Contreras, R.H., Peralta, J.E. Anomeric effect on geminal and vicinal JHH NMR coupling constants. J Phys Chem A. 2004;108(38):7762-7768.
http://dx.doi.org/10.1021/jp047226z