Theoretical study of inversion and topomerization processes of substituted cyclohexanes: The relevance of the energy 3D hypersurface

ChemPhysChem

Volumn 6, Issue 4, 2005, Pages 671-680

  Fernández Alonso, María Del Carmen ^a   Cañada, Javier ^b   Jiménez Barbero, Jesús ^b   Cuevas, Gabriel ^a  

^a UNIVERSIDAD NACIONAL AUTÓNOMA DE MÉXICO   (Mexico)

^b CENTRO DE INVESTIGACIONES BIOLÓGICAS   (Spain)

Author keywords

Conformation analysis; Cyclohexane; Density functional calculations; Inversion topomerization; Transition states

Indexed keywords

CYCLOHEXANE; DENSITY FUNCTIONAL THEORY; MOLECULAR PHYSICS; QUANTUM CHEMISTRY;

CONFORMATION ANALYSIS; DIMENSIONAL REPRESENTATION; EFFECT OF SUBSTITUTION; INVERSION/TOPOMERIZATION; MOLECULAR REACTIVITY; MOLECULAR SYMMETRY; REACTION MECHANISM; TRANSITION STATE;

POTENTIAL ENERGY;

EID: 17744396932     PISSN: 14394235     EISSN: None     Source Type: Journal    
DOI: 10.1002/cphc.200400495     Document Type: Article

References (57)

1. a) D. H. R. Barton, Experientia 1950, 6, 316;
2. b) S. Winstein, N. J. Holness, J. Am. Chem. Soc. 1955, 77, 5562;
3. c) E. L. Eliel, R. S. Ro, J. Am. Chem. Soc. 1957, 79, 5986 and 5992.
4. E. L. Eliel, N. L. Alinger, S. J. Angyal, Conformational Analysis, Wiley, New York, 1965.
5. E. L. Eliel, S. H. Wilen, Stereochemistry of Organic Compounds, Wiley, New York, 1994.
6. E. Juaristi, Conformational Behavior of Six-Membered Rings, VCH, New York, 1995.
7. a) U. Salzner, P. V. R. Schleyer, J. Org. Chem. 1994, 59, 2138;
8. b) C. W. Beckett, K. S. Pitzer, R. Spitzer, J. Am. Chem. Soc. 1947, 69, 2488.
9. a) J. B. Hendrickson, J. Am. Chem. Soc. 1967, 89, 7047;
10. b) D. Cremer, J. Pople, J. Am. Chem. Soc. 1975, 97, 1354.
11. M. C. Fernández-Alonso, J. L. Asensio, F. J. Cañada, J. Jiménez-Barbero, G. Cuevas, ChemPhysChem 2003, 4, 754.
12. M. B. Smith, J. March, March's Advanced Organic Chemistry, 5th ed., Wiley, New York, 2001, p. 173.
13. F. Cortés-Guzmán, J. Hernández-Trujillo, G. Cuevas, J. Phys. Chem. A 2003, 107, 9253.
14. K. B. Wiberg, H. Castejon, W. F. Bailey, J. Ochterski, J. Org. Chem. 2000, 65, 1181, and references therein.
15. I. Abe, Y. Sakano, M. Sodeyama, H. Tanaka, H. Nagouchi, M. Shibuya, Y. Ebizuka, J. Am. Chem. Soc. 2004, 126, 6880.
16. A. García-Herrero, E. Montera, J. L. Muñoz, J. F. Espinosa, A. Vián, J. L. Garcia, J. L. Asensio, F. J. Canãda, J. Jiménez-Barbero, J. Am. Chem. Soc. 2002, 124, 4804.
17. For reviews on the anomeric effect, see a) Anomeric Effect: Origin and Consequences (Eds.: W. A. Szarek, D. Horton), ACS Symposium Series No. 87, American Chemical Society, Washington, 1979; b) A. J. Kirby, The Anomeric Effect and Related Stereoelectronic Effects at Oxygen, Springer, New York, 1983; c) E. Juaristi, G. Cuevas, Tetrahedron 1992, 48, 5019; d) The Anomeric and Associated Stereoelectronic Effects (Ed.: G. R. J. Thatcher), American Chemical Society, Washington, 1993; e) P. Graczyk, M. Mikolajczyk, Top. Stereochem. 1994, 21, 159; f) E. Juaristi, G. Cuevas, The Anomeric Effect, CRC Press, Boca Raton, 1995; g) J. Chattopadhyaya, Stereoelectronic Effects in Nucleosides and Their Structural Implications, Uppsala University Press, Uppsala, 1999; h) C. L. Perrin, Acc. Chem. Res. 2002, 35, 28.
18. For reviews on the anomeric effect, see a) Anomeric Effect: Origin and Consequences (Eds.: W. A. Szarek, D. Horton), ACS Symposium Series No. 87, American Chemical Society, Washington, 1979; b) A. J. Kirby, The Anomeric Effect and Related Stereoelectronic Effects at Oxygen, Springer, New York, 1983; c) E. Juaristi, G. Cuevas, Tetrahedron 1992, 48, 5019; d) The Anomeric and Associated Stereoelectronic Effects (Ed.: G. R. J. Thatcher), American Chemical Society, Washington, 1993; e) P. Graczyk, M. Mikolajczyk, Top. Stereochem. 1994, 21, 159; f) E. Juaristi, G. Cuevas, The Anomeric Effect, CRC Press, Boca Raton, 1995; g) J. Chattopadhyaya, Stereoelectronic Effects in Nucleosides and Their Structural Implications, Uppsala University Press, Uppsala, 1999; h) C. L. Perrin, Acc. Chem. Res. 2002, 35, 28.
19. For reviews on the anomeric effect, see a) Anomeric Effect: Origin and Consequences (Eds.: W. A. Szarek, D. Horton), ACS Symposium Series No. 87, American Chemical Society, Washington, 1979; b) A. J. Kirby, The Anomeric Effect and Related Stereoelectronic Effects at Oxygen, Springer, New York, 1983; c) E. Juaristi, G. Cuevas, Tetrahedron 1992, 48, 5019; d) The Anomeric and Associated Stereoelectronic Effects (Ed.: G. R. J. Thatcher), American Chemical Society, Washington, 1993; e) P. Graczyk, M. Mikolajczyk, Top. Stereochem. 1994, 21, 159; f) E. Juaristi, G. Cuevas, The Anomeric Effect, CRC Press, Boca Raton, 1995; g) J. Chattopadhyaya, Stereoelectronic Effects in Nucleosides and Their Structural Implications, Uppsala University Press, Uppsala, 1999; h) C. L. Perrin, Acc. Chem. Res. 2002, 35, 28.
20. For reviews on the anomeric effect, see a) Anomeric Effect: Origin and Consequences (Eds.: W. A. Szarek, D. Horton), ACS Symposium Series No. 87, American Chemical Society, Washington, 1979; b) A. J. Kirby, The Anomeric Effect and Related Stereoelectronic Effects at Oxygen, Springer, New York, 1983; c) E. Juaristi, G. Cuevas, Tetrahedron 1992, 48, 5019; d) The Anomeric and Associated Stereoelectronic Effects (Ed.: G. R. J. Thatcher), American Chemical Society, Washington, 1993; e) P. Graczyk, M. Mikolajczyk, Top. Stereochem. 1994, 21, 159; f) E. Juaristi, G. Cuevas, The Anomeric Effect, CRC Press, Boca Raton, 1995; g) J. Chattopadhyaya, Stereoelectronic Effects in Nucleosides and Their Structural Implications, Uppsala University Press, Uppsala, 1999; h) C. L. Perrin, Acc. Chem. Res. 2002, 35, 28.
21. For reviews on the anomeric effect, see a) Anomeric Effect: Origin and Consequences (Eds.: W. A. Szarek, D. Horton), ACS Symposium Series No. 87, American Chemical Society, Washington, 1979; b) A. J. Kirby, The Anomeric Effect and Related Stereoelectronic Effects at Oxygen, Springer, New York, 1983; c) E. Juaristi, G. Cuevas, Tetrahedron 1992, 48, 5019; d) The Anomeric and Associated Stereoelectronic Effects (Ed.: G. R. J. Thatcher), American Chemical Society, Washington, 1993; e) P. Graczyk, M. Mikolajczyk, Top. Stereochem. 1994, 21, 159; f) E. Juaristi, G. Cuevas, The Anomeric Effect, CRC Press, Boca Raton, 1995; g) J. Chattopadhyaya, Stereoelectronic Effects in Nucleosides and Their Structural Implications, Uppsala University Press, Uppsala, 1999; h) C. L. Perrin, Acc. Chem. Res. 2002, 35, 28.
22. For reviews on the anomeric effect, see a) Anomeric Effect: Origin and Consequences (Eds.: W. A. Szarek, D. Horton), ACS Symposium Series No. 87, American Chemical Society, Washington, 1979; b) A. J. Kirby, The Anomeric Effect and Related Stereoelectronic Effects at Oxygen, Springer, New York, 1983; c) E. Juaristi, G. Cuevas, Tetrahedron 1992, 48, 5019; d) The Anomeric and Associated Stereoelectronic Effects (Ed.: G. R. J. Thatcher), American Chemical Society, Washington, 1993; e) P. Graczyk, M. Mikolajczyk, Top. Stereochem. 1994, 21, 159; f) E. Juaristi, G. Cuevas, The Anomeric Effect, CRC Press, Boca Raton, 1995; g) J. Chattopadhyaya, Stereoelectronic Effects in Nucleosides and Their Structural Implications, Uppsala University Press, Uppsala, 1999; h) C. L. Perrin, Acc. Chem. Res. 2002, 35, 28.
23. For reviews on the anomeric effect, see a) Anomeric Effect: Origin and Consequences (Eds.: W. A. Szarek, D. Horton), ACS Symposium Series No. 87, American Chemical Society, Washington, 1979; b) A. J. Kirby, The Anomeric Effect and Related Stereoelectronic Effects at Oxygen, Springer, New York, 1983; c) E. Juaristi, G. Cuevas, Tetrahedron 1992, 48, 5019; d) The Anomeric and Associated Stereoelectronic Effects (Ed.: G. R. J. Thatcher), American Chemical Society, Washington, 1993; e) P. Graczyk, M. Mikolajczyk, Top. Stereochem. 1994, 21, 159; f) E. Juaristi, G. Cuevas, The Anomeric Effect, CRC Press, Boca Raton, 1995; g) J. Chattopadhyaya, Stereoelectronic Effects in Nucleosides and Their Structural Implications, Uppsala University Press, Uppsala, 1999; h) C. L. Perrin, Acc. Chem. Res. 2002, 35, 28.
24. For reviews on the anomeric effect, see a) Anomeric Effect: Origin and Consequences (Eds.: W. A. Szarek, D. Horton), ACS Symposium Series No. 87, American Chemical Society, Washington, 1979; b) A. J. Kirby, The Anomeric Effect and Related Stereoelectronic Effects at Oxygen, Springer, New York, 1983; c) E. Juaristi, G. Cuevas, Tetrahedron 1992, 48, 5019; d) The Anomeric and Associated Stereoelectronic Effects (Ed.: G. R. J. Thatcher), American Chemical Society, Washington, 1993; e) P. Graczyk, M. Mikolajczyk, Top. Stereochem. 1994, 21, 159; f) E. Juaristi, G. Cuevas, The Anomeric Effect, CRC Press, Boca Raton, 1995; g) J. Chattopadhyaya, Stereoelectronic Effects in Nucleosides and Their Structural Implications, Uppsala University Press, Uppsala, 1999; h) C. L. Perrin, Acc. Chem. Res. 2002, 35, 28.
25. a) S. Wolfe, A. Rauk, L. M. Tel, I. G. Csizmadia, J. Chem. Soc. 1971, 136;
26. b) S. Wolfe, Acc. Chem. Res. 1972, 5, 102.
27. a) F. Freeman, C. Cha, Int. J. Quant. Chem. 2004, 96, 443;
28. b) F. Freeman, C. Cha, J. Phys. Org. Chem. 2004, 17, 32;
29. c) F. Freeman, K. T. Lee, J. Phys. Chem. A 2003, 107, 2908;
30. d) F. Freeman, E. Dereck, Struct. Chem. 2003, 14, 497;
31. e) F. Freeman, E. Dereck, J. Comp. Chem. 2003, 24, 909;
32. f) F. Freeman, F. Gomarooni, W. J. Hehre, Struct. Chem. 2002, 13, 115.
33. 2, which gives an identical product in which, however, the two methyl groups are interchanged. Also called "automerization" or "degenerate isomerization". The two structures that are interconverted may be called "topomers". See ref. [3], p. 1210.
34. a) A. Streitwieser, C. H. Heathcock, E. M. Kosower, Introduction to Organic Chemistry, 4th ed., Macmillan, New York, 1992;
35. b) E. L. Eliel, Stereochemistry of Carbon Compounds, McGraw-Hill, New York, 1962;
36. c) E. L. Eliel, N. L. Allinger, S. J. Angyal, G. A. Morrison, Conformational Analysis, Wiley, New York, 1965;
37. d) M. Hanack, Conformational Theory, Academic Press, New York, 1965;
38. e) K. Mislow, Introduction to Stereochemistry, Benjamin, New York, 1966;
39. f) J. F. Stoddart, Stereochemistry of Carbohydrates, Wiley, New York, 1971;
40. g) J. Dale, Stereochemistry and Conformational Analysis, Verlag Chemie, Weinheim, 1978.
41. D. Cramer, K. J. Szabo in Conformational Behavior of Six-Member Rings (Ed.: E. Juaristi), VCH, New York, 1995, p. 97.
42. a) O. Ermer, P. M. Ivanov, ; E. Osawa, J. Comput. Chem. 1985, 6, 401;
43. b) I. Kolossváry, W. C. Guida, J. Am. Chem. Soc. 1993, 115, 2107.
44. H. Booth, J. R. Everett, J. Chem. Soc. Perkin Trans. 2, 1980, 255.
45. C. W. Beckett, K. S. Pitzar, R. Spitzer, J. Am. Chem. Soc. 1947, 69, 2488.
46. K. B. Wiberg, M. A. Murcko, J. Am. Chem. Soc. 1988, 110, 8029.
47. A. E. Aliev, K. D. M. Harris, J. Am. Chem. Soc. 1993, 115, 6369.
48. M. E. Squillacote, R. S. Sheridan, O. L. Chapman, F. A. L. Anet, J. Am. Chem. Soc. 1975, 97, 3244.
49. J. B. Lambert, C. E. Mixon, D. H. Jonson, J. Am. Chem. Soc. 1973, 95, 4634.
50. Gaussian 98 (Revision A.11.3) M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petterson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foreswman, J. Cioslowski, J. V. Ortiz, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. G. Johnson, W. Chen, M. W. Wong, J. L. Andres, M. Head-Gordon, E. S. Replogle, J. A. Pople, Gaussian, Inc., Pittsburgh, PA, 1998.
51. B. J. Lynch, P. L. Fast, M. Harris, D. G. Truhlar, J. Phys. Chem. A. 2000, 104, 4811.
52. A. D. Becke, J. Chem. Phys. 1993, 98, 5648.
53. a) C. Moller, M. S. Plesset, Phys. Rev. 1934, 46, 618;
54. b) M. J. Frish, M. Head-Gordon, J. A. Pople, Chem. Phys. Lett. 1990, 166, 281.
55. L. A. Curtiss, K. Raghavachari, G. W. Trucks, J. A. Pople, J. Chem. Phys. 1991, 94, 7221.
56. a) C. González, H. B. Schlegel, J. Chem. Phys. 1989, 90, 2154;
57. b) C. González, H. B. Schlegel, J. Chem. Phys. 1991, 95, 5853.