Artículo
Pérez, C.; Suardíaz, R.; Ortiz, P.J.; Crespo-Otero, R.; Bonetto, G.M.; Gavín, J.A.; De La Vega García, J.M.; San Fabián, J.; Contreras, R.H. "On the unusual 2JC2-Hf coupling dependence on syn/anti CHO conformation in 5-X-furan-2-carboxaldehydes" (2008) Magnetic Resonance in Chemistry. 46(9):846-850
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Abstract:
A remarkable difference for 2JC2-H f, coupling constant in syn and anti conformers of 5-X-furan-2-carboxaldehydes (X = CH3, Ph, NO2, Br) and a rationalization of this difference are reported. On the basis of the current knowledge of the Fermi-contact term transmission, a rather unusual dual-coupling pathway in the syn conformer is presented. The additional coupling pathway resembles somewhat that of the JH-H in homoallylic couplings, which are transmitted by hyperconjugative interactions involving the πC=C electronic system. The homoallylic coupling pathway can be labeled as σ*C-H ←-πc=c → σ*C-H. In the present case, this additional coupling pathway, using an analogous notation, can be labeled as σ* c2-cc ← LP1(O 1)⋯ LP2(Oc) → σ* Cc-Hf (σ*C2 -C c) where O1 and Oc stand for the ring and carbonyl O atoms, respectively. This additional coupling pathway is not activated in the anti conformers since both oxygen lone pairs do not overlap. Copyright © 2008 John Wiley & Sons, Ltd.
Registro:
| Documento: | Artículo |
| Título: | On the unusual 2JC2-Hf coupling dependence on syn/anti CHO conformation in 5-X-furan-2-carboxaldehydes |
| Autor: | Pérez, C.; Suardíaz, R.; Ortiz, P.J.; Crespo-Otero, R.; Bonetto, G.M.; Gavín, J.A.; De La Vega García, J.M.; San Fabián, J.; Contreras, R.H. |
| Filiación: | Departamento de Química Física, Facultad de Química, Universidad de la Habana, La Habana 10400, Cuba Laboratorio de Química Computational y Teórica, Facultad de Química, Universidad de la Habana, La Habana 10400, Cuba Instituto Universitario de Bioorgánica Antonio González, Universidad de la Laguna, Santa Cruz de Tenerife, Spain Departamento de Quimica Física Aplicada, Facultad de Ciencias, Universidad Autónoma de Madrid, Madrid 28049, Esparto, Spain Departamento de Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires and CONICET, Buenos Aires, Argentina |
| Palabras clave: | Fermi-contact transmission; Furfural; Geminal NMR couplings; NBO; Through space; aldehyde; furan derivative; article; chemical model; chemistry; conformation; electron; methodology; nuclear magnetic resonance spectroscopy; quantum theory; standard; stereoisomerism; Aldehydes; Electrons; Furans; Magnetic Resonance Spectroscopy; Models, Chemical; Molecular Conformation; Quantum Theory; Reference Standards; Stereoisomerism |
| Año: | 2008 |
| Volumen: | 46 |
| Número: | 9 |
| Página de inicio: | 846 |
| Página de fin: | 850 |
| DOI: | http://dx.doi.org/10.1002/mrc.2268 |
| Título revista: | Magnetic Resonance in Chemistry |
| Título revista abreviado: | Magn. Reson. Chem. |
| ISSN: | 07491581 |
| CODEN: | MRCHE |
| CAS: | Aldehydes; Furans |
| Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_07491581_v46_n9_p846_Perez |
Referencias:
- Karabatsos, G.J., Vane, F.M., (1963) J. Am. Chem. Soc, 85, p. 3886
- Dahlqvist, K.-I., Forsén, S., (1965) J. Phys. Chem, 69, p. 1760
- Dahlqvist, K.-I., Forsen, S., (1965) J. Phys. Chem, 69, p. 4062
- Wasylishen, R., Schaefer, T., (1971) Can. J. Chem, 49, p. 3216
- Katritzky, A.R., Akhmedov, N.G., Doskocz, J., Mohapatra, P.P., Hall, C.D., Güven, A., (2007) Magn. Reson. Chem, 45, p. 532
- Soncini, A., Lazzeretti, P., (2003) J. Chem. Phys, 119, p. 1343
- Castillo, N., Malta, C.F., Boyd, R.J., (2005) J. Chem. Inf. Model, 45, p. 354
- Weinhold, F., (1998) Encyclopedia of Computational Chemistry, 3, p. 1792. , Ed: Pv. R. Schleyer, Wiley: New York
- Reed, A.E., Curtiss, L.A., Weinhold, F., (1988) Chem. Rev, 88, p. 899
- Contreras, R.H., Esteban, A.L., Diez, E., Head, N.J., Della, E.W., (2006) Mol. Phys, 104, p. 485
- Contreras, R.H., Peralta, J.E., (2000) Prog. NMR Spectrosc, 37, p. 321
- Tormena, C.F., Vilcachagua, J.D., Karcher, V., Rittner, R., Contreras, R.H., (2007) Magn. Reson. Chem, 45, p. 590
- Contreras, R.H., Esteban, A.L., Diez, E., Della, E.W., Lochert, I.J., dos Santos, F.P., Tormena, C.F., (2006) J. Phys. Chem. A, 110, p. 4266
- Tormena, C.F., Rittner, R., Contreras, R.H., Peralta, J.E., (2004) J. Phys. Chem. A, 108, p. 7762
- Williamson, R.T., Marquez, B.L., Gerwick, W.H., Kövér, K.E., (2000) Magn. Reson. Chem, 38, p. 265
- Gaussian 03, Revision C.02, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr, T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. C; Mennucci, B., Tomasi, J., (1997) J. Chem. Phys, 106, p. 5151
- Cossi, M., Barone, V., Mennucci, B., Tomasi, J., (1998) Chem. Phys. Lett, 286, p. 253
- Zaccari, D., Barone, V., Peralta, J.E., Contreras, R.H., Taurian, O.E., Diez, E., Esteban, A., (2003) Int. J. Mol. Sci, 4, p. 93
- Kaski, J., Lantto, P., Vaara, J., Jokisaari, J., (1998) J. Am. Chem. Soc, 120, p. 3393
- Hobgood Jr, R.T., Goldstein, J.H., (1964) J. Mol. Spectrosc, 12, p. 76
- Ernst, L., Wray, V., Chertkov, V.A., Sergeyev, N.M., (1977) J. Magn. Reson, 25, p. 123
- Harris, R.K., Ng, S., Connelly, A., (1991) Magn. Reson. Chem, 29, p. 1152
- Hansen, P.E., Berg, A., (1983) Spectrosc. Int. J, 2, p. 1
- Facelli, J.C., Grant, D.M., (1987) Theor. Chim. Acta, 71, p. 277
- Contreras, R.H., Taurian, O.E., Ortiz, F.S., Peralta, J.E., (2000) J. Mol. Struct, 556, p. 263
- Hansen, P.E., Poulsen, O.K., Berg, A., (1977) Org. Magn. Reson, 9, p. 649
- Hansen, P.E., Berg, A., Schaumburg, K., (1987) Magn. Reson. Chem, 25, p. 508
- Pedersoli, S., Dos Santos, F.P., Rinner, R., Contreras, R.H., Tormena, C.F., (2008) Magn. Reson. Chem, 46, p. 202
- Bondi, A., (1964) J. Phys. Chem, 68, p. 441
- Alkorta, I., Elguero, J., (2004) Struct. Chem, 15, p. 117
- Bader, R.F.W., (1990) Atoms in Molecules: A Quantum Theory, , Oxford University Press: Oxford
- Arnold, W.D., Olfield, E., (2000) J. Am. Chem. Soc, 122, p. 12835
- Taurian, O.E., De Kowalewski, D.G., Pérez, J.E., Contreras, R.H., (2005) J. Mol. Struct, 754, p. 1
Citas:
---------- APA ----------
Pérez, C., Suardíaz, R., Ortiz, P.J., Crespo-Otero, R., Bonetto, G.M., Gavín, J.A., De La Vega García, J.M.,..., Contreras, R.H. (2008) . On the unusual 2JC2-Hf coupling dependence on syn/anti CHO conformation in 5-X-furan-2-carboxaldehydes. Magnetic Resonance in Chemistry, 46(9), 846-850.http://dx.doi.org/10.1002/mrc.2268
---------- CHICAGO ----------
Pérez, C., Suardíaz, R., Ortiz, P.J., Crespo-Otero, R., Bonetto, G.M., Gavín, J.A., et al. "On the unusual 2JC2-Hf coupling dependence on syn/anti CHO conformation in 5-X-furan-2-carboxaldehydes" . Magnetic Resonance in Chemistry 46, no. 9 (2008) : 846-850.http://dx.doi.org/10.1002/mrc.2268
---------- MLA ----------
Pérez, C., Suardíaz, R., Ortiz, P.J., Crespo-Otero, R., Bonetto, G.M., Gavín, J.A., et al. "On the unusual 2JC2-Hf coupling dependence on syn/anti CHO conformation in 5-X-furan-2-carboxaldehydes" . Magnetic Resonance in Chemistry, vol. 46, no. 9, 2008, pp. 846-850.http://dx.doi.org/10.1002/mrc.2268
---------- VANCOUVER ----------
Pérez, C., Suardíaz, R., Ortiz, P.J., Crespo-Otero, R., Bonetto, G.M., Gavín, J.A., et al. On the unusual 2JC2-Hf coupling dependence on syn/anti CHO conformation in 5-X-furan-2-carboxaldehydes. Magn. Reson. Chem. 2008;46(9):846-850.http://dx.doi.org/10.1002/mrc.2268
