Theoretical Studies of Eliminations. 6. The Regiochemistry and Stereochemistry of the Gas-Phase Reactions of 3-Halocyclohexenes with Fluoride. An ab Initia Study

Journal of Organic Chemistry

Volumn 62, Issue 23, 1997, Pages 7991-8000

  Gronert, Scott ^a   Kass, Steven R ^b  

^a SAN FRANCISCO STATE UNIVERSITY   (United States)

^b University of Minnesota   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 1542709799     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo970626g     Document Type: Article

References (64)

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41. rxn value of approximately +11 kcal/mol is calculated for the gas phase reaction.
42. GAUSSIAN92: Frisch, M. J.; Trucks, G. W.; Head-Gordon, M.; Gill, P. M. W.; Wong, M. H.; Foresman, J. B.; Johnson, B. D.; Schlegel, H. B.; Robb, M. A.; Replogle, E. S.; Gomperts, R.; Anfres, J. L.; Raghavachari, K.; Binkley, J. S.; Gonzalez, C.; Martin, R. L.; Fox, D. J.; DeFrees, D. J.; Baker, J. J. P.; Pople, J. A., Gaussian, Inc., Pittsburgh, PA, 1992.
43. GAUSSIAN94: Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Kieth, T. A.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Cioslowski, J.; Stefanov, B. B.; Nanayakkara, A.; Challacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; DeFrees, D. J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A., Gaussian, Inc., Pittsburgh, PA, 1995.
44. Basis sets were taken from the libraries present in GAUSSIAN92 and GAUSSIAN94.
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46. In the text and tables, energies are referenced to the most stable conformation of the 3-halocyclohexene (equatorial). The difference in energy between the axial and equatorial conformations is small (<1 kcal/mol) for both systems.
47. β is the olefinic carbon in 1,4-eliminations and the methylene carbon in 1,2-eliminations.
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52. Kass, S. R., unpublished results.
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56. At the MP2 level, this transition state could not be located in an automated transition state search. Instead, the transition state was located by manually varying the breaking C-F distance while optimizing all other geometric parameters.
57. This situation suggests that in reactions that require the formation of a product complex, the true dynamic bottleneck may occur after the calculated transition state and involve the complexation process to some extent. Therefore, an interaction between the leaving group and the protonated base is not required in the transition state (electronic potential energy surface). It should be noted that anti elimination can also lead to complexed products so complexation cannot be used to distinguish between anti and syn mechanisms.
58. If complexation occurs, the elimination is exothermic by approximately 34 kcal/mol Wenthold, P. G.; Squires, R. R. J. Phys. Chem. 1995, 99, 2002.
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63. Entropy estimates derived from G94 frequency calculations should be viewed with caution because they contain strong contributions from low frequency modes that are not well characterized by this approach.
64. The entropy differences between the various elimination path-ways are relatively small.