An ab initio study of SN2 reactivity at C6 in hexopyranose derivatives. I. Influence of dipole-dipole interactions in the transition structure

Journal of Physical Chemistry A

Volumn 109, Issue 1, 2005, Pages 213-217

  Dawes, Richard ^a   Gough, Kathleen M ^a   Hultin, Philip G ^a  

^a UNIVERSITY OF MANITOBA   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

DIPOLE-DIPOLE INTERACTIONS; GALACTO-CONFIGURED SULFONATES; HEXOPYRANOSE DERIVATIVES; TRANSITION STRUCTURE;

CHEMICAL BONDS; CHEMICAL REACTIONS; CHLORIDE MINERALS; ELECTRIC CHARGE; FLUORINE; HYDROXYLATION; INTEGRATION; MATHEMATICAL MODELS;

DERIVATIVES;

CARBOHYDRATE; CARBON;

ARTICLE; CHEMICAL STRUCTURE; CHEMISTRY; COMPUTER SIMULATION;

CARBOHYDRATES; CARBON; COMPUTER SIMULATION; MODELS, MOLECULAR; MOLECULAR STRUCTURE;

EID: 12344277804     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp0372892     Document Type: Article

References (20)

1. Hase, W. L.; Sun, L.; Song, K. Science 2002, 296, 875.
2. Regan, C. K.: Craig, S. L.; Brauman, J. I. Science 2002, 295, 2245-2247.
3. Ball, D. H.: Parrish, F. W. Adv. Carbohydr. Chem. Biochem. 1969, 24, 139-197.
4. Wu, M.-C.; Andersen, L.; Slife, C. W.; Jensen, L. J. J. Org. Chem. 1974. 39, 3014-3020.
5. (a) Mulard, L. A.; Kovác, P.; Glaudemans, C. P. J. Carbohydr. Res. 1994, 259, 117-119.
6. (b) Ali, M. A.: Hough, L.; Richardson, A. C. Carbohvdr. Res. 1991, 216, 271-287.
7. Richardson, A. C. Carbohydr. Res. 1969, 10, 395-402.
8. Collins, P. M.; Ferrier, R. J. Monosaccharides, Their Chemistry and Their Kotes in Natural Products: Wiley: Chichester, 1995.
9. Seehach, D.; Chow, H.-F.; Jackson, R. F. W.; Sutter, M. A.; Thaisrivongs, S.: Zimmermann, J. Liebigs Ann. Chem. 1986, 1281-1308.
10. Craig, S. L.; Brauman, J. I. J. Am. Chem. Soc., 1999, 121, 6690-6699.
11. Boyd, R. J.; Boyd, S. L. J. Am. Chem. Soc. 1992, 114. 1652-1655.
12. Frisch, M. J.: Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A.; Stratmann, R. E.: Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.: Cossi, M.; Cammi R.: Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochlerski, J. Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K. Rabuck, A. D.: Raghavachari, K.; Foresman, J. B.; Cioslowski, J.: Ortiz, J V.: Stefanov, B. B.: Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I. Gomperts, R.; Martin, R. L.: Fox, D. J.; Keith, T.: Al-Laham, M. A.,: Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B. G.; Chen, W.; Wong, M. W.; Andres, J. L.; Head-Gordon, M.; Replogle, E. S.; Pople. J. A. Gaussion 98W. Revision A.7 or A. 11 [parallel: Gaussian, Inc.: Pittsburgh, PA, 1998.
13. Biegler-König, F.; Schönbohm, J.; Bayles, D. J. Comput. Chem. 2001, 22, 545-559.
14. (a) Becke, A. D. J. Chem. Phys. 1993,98,5648-5652.
15. (b) Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.; Frisch. M. J. J. Phys. Chem. 1994, 98, 11623-11627.
16. Bader, R. F. W. Atoms in Molecules: a Quantum Theory; The International Series of Monographs on Chemistry 22; Clarendon Press: Oxford, 1990.
17. Aicken, F. M.: Popelier, P. L. A. Can. J. Chem. 2000, 78, 415-426.
18. (a) Lee, I.; Kim, C. K.; Chung, D. S.; Lee, B.-S. J. Org. Chem. 1994, 59, 4490-4494.
19. (b) Streitwieser, A.; Choy, G. S.-C.; Abu-Hasanayn, F. J. Am. Chem. Soc. 1997, 119, 5013-5019.
20. In the AIM formalism, although the total molecular energy is recovered by summing the atomic contributions, the recovery of molecular dipoles is less straightforward. Because the charge is partitioned into atomic basins, each "atom" has a net charge (summing to zero for a neutral molecule) and an atomic dipole representing asymmetry of charge within the atomic basin. To recover a molecular dipole from atomic charges and dipoles, the contribution from the relative positions of the charged nuclear attractors is added to that of the sum of the atomic dipoles (ref 14). When a dipole is induced by a perturbation such as an applied field, or as in our case the change of conformation, there are two possible contributions. The atomic dipoles representing distortion of charge within the basins change. There is also a change in the charge-separation term that includes transfer of charge across the interatomic boundary, changing the amount of charge being separated, and geometry relaxations that change the distance by which charge is separated. The charge-separation contribution to the dipole is directed precisely between the two nuclear attractors, while in general, the atomic dipole contribution can be in any direction.