Effect of olefin pyramidalization on the proton affinity of tricyclo[3.3.3.03,7]undec-3(7)-ene as determined by ab initio calculations and kinetic method measurements

Journal of the American Chemical Society

Volumn 118, Issue 44, 1996, Pages 10872-10878

  Cleven, Curtis D ^a   Hoke II, Steven H ^a   Cooks, R Graham ^a   Hrovat, David A ^b   Smith, Joseph M ^b   Lee, Ming Shi ^b   Borden, Westen Thatcher ^b  

^a PURDUE UNIVERSITY   (United States)

^b UNIVERSITY OF WASHINGTON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

POLYCYCLIC HYDROCARBON;

ARTICLE; DRUG STRUCTURE; MOLECULAR DYNAMICS; THEORY; THERMODYNAMICS;

EID: 0029795082     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja960776t     Document Type: Article

References (66)

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10. For n = 1, see: (a) Renzoni, G. E.; Yin, T.-K.; Borden, W. T. J. Am. Chem. Soc. 1986, 108, 7121. (b) Radziszewski, J. G.; Yin, T.-K.; Renzoni, G. E.; Hrovat, D. A.; Borden, W. T.; Michl, J. J. Am. Chem. Soc. 1993, 115, 1454. For n = 2, see: (c) Renzoni, G. E.; Yin, T.-K.; Miyake, F.; Borden, W. T. Tetrahedron 1986, 42, 1581. (d) Radziszewski, J. G.; Yin, T.-K.; Miyake, F.; Renzoni, G. E.; Borden, W. T.; Michl, J. J. Am. Chem. Soc. 1986, 108, 3544. (e) Yin, T.-K.; Radziszewski, J. G.; Renzoni, G. E.; Downing, J. W.; Michl, J.; Borden, W. T. J. Am. Chem. Soc. 1987, 109, 820. A bis-ethano derivative of n = O has been prepared: (f) Branan, B. M.; Paquette, L. A.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1992, 114, 774. Generation of a dimethyl derivative has also been reported: (g) Camps, P.; Font- Bardi, M.; Pérez, F.; Solans, X.; Vázquez, S. Angew. Chem., Int. Ed. Engl. 1995, 34, 912.
11. For n = 1, see: (a) Renzoni, G. E.; Yin, T.-K.; Borden, W. T. J. Am. Chem. Soc. 1986, 108, 7121. (b) Radziszewski, J. G.; Yin, T.-K.; Renzoni, G. E.; Hrovat, D. A.; Borden, W. T.; Michl, J. J. Am. Chem. Soc. 1993, 115, 1454. For n = 2, see: (c) Renzoni, G. E.; Yin, T.-K.; Miyake, F.; Borden, W. T. Tetrahedron 1986, 42, 1581. (d) Radziszewski, J. G.; Yin, T.-K.; Miyake, F.; Renzoni, G. E.; Borden, W. T.; Michl, J. J. Am. Chem. Soc. 1986, 108, 3544. (e) Yin, T.-K.; Radziszewski, J. G.; Renzoni, G. E.; Downing, J. W.; Michl, J.; Borden, W. T. J. Am. Chem. Soc. 1987, 109, 820. A bis-ethano derivative of n = O has been prepared: (f) Branan, B. M.; Paquette, L. A.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1992, 114, 774. Generation of a dimethyl derivative has also been reported: (g) Camps, P.; Font- Bardi, M.; Pérez, F.; Solans, X.; Vázquez, S. Angew. Chem., Int. Ed. Engl. 1995, 34, 912.
12. For n = 1, see: (a) Renzoni, G. E.; Yin, T.-K.; Borden, W. T. J. Am. Chem. Soc. 1986, 108, 7121. (b) Radziszewski, J. G.; Yin, T.-K.; Renzoni, G. E.; Hrovat, D. A.; Borden, W. T.; Michl, J. J. Am. Chem. Soc. 1993, 115, 1454. For n = 2, see: (c) Renzoni, G. E.; Yin, T.-K.; Miyake, F.; Borden, W. T. Tetrahedron 1986, 42, 1581. (d) Radziszewski, J. G.; Yin, T.-K.; Miyake, F.; Renzoni, G. E.; Borden, W. T.; Michl, J. J. Am. Chem. Soc. 1986, 108, 3544. (e) Yin, T.-K.; Radziszewski, J. G.; Renzoni, G. E.; Downing, J. W.; Michl, J.; Borden, W. T. J. Am. Chem. Soc. 1987, 109, 820. A bis-ethano derivative of n = O has been prepared: (f) Branan, B. M.; Paquette, L. A.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1992, 114, 774. Generation of a dimethyl derivative has also been reported: (g) Camps, P.; Font- Bardi, M.; Pérez, F.; Solans, X.; Vázquez, S. Angew. Chem., Int. Ed. Engl. 1995, 34, 912.
13. For n = 1, see: (a) Renzoni, G. E.; Yin, T.-K.; Borden, W. T. J. Am. Chem. Soc. 1986, 108, 7121. (b) Radziszewski, J. G.; Yin, T.-K.; Renzoni, G. E.; Hrovat, D. A.; Borden, W. T.; Michl, J. J. Am. Chem. Soc. 1993, 115, 1454. For n = 2, see: (c) Renzoni, G. E.; Yin, T.-K.; Miyake, F.; Borden, W. T. Tetrahedron 1986, 42, 1581. (d) Radziszewski, J. G.; Yin, T.-K.; Miyake, F.; Renzoni, G. E.; Borden, W. T.; Michl, J. J. Am. Chem. Soc. 1986, 108, 3544. (e) Yin, T.-K.; Radziszewski, J. G.; Renzoni, G. E.; Downing, J. W.; Michl, J.; Borden, W. T. J. Am. Chem. Soc. 1987, 109, 820. A bis-ethano derivative of n = O has been prepared: (f) Branan, B. M.; Paquette, L. A.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1992, 114, 774. Generation of a dimethyl derivative has also been reported: (g) Camps, P.; Font- Bardi, M.; Pérez, F.; Solans, X.; Vázquez, S. Angew. Chem., Int. Ed. Engl. 1995, 34, 912.
14. For n = 1, see: (a) Renzoni, G. E.; Yin, T.-K.; Borden, W. T. J. Am. Chem. Soc. 1986, 108, 7121. (b) Radziszewski, J. G.; Yin, T.-K.; Renzoni, G. E.; Hrovat, D. A.; Borden, W. T.; Michl, J. J. Am. Chem. Soc. 1993, 115, 1454. For n = 2, see: (c) Renzoni, G. E.; Yin, T.-K.; Miyake, F.; Borden, W. T. Tetrahedron 1986, 42, 1581. (d) Radziszewski, J. G.; Yin, T.-K.; Miyake, F.; Renzoni, G. E.; Borden, W. T.; Michl, J. J. Am. Chem. Soc. 1986, 108, 3544. (e) Yin, T.-K.; Radziszewski, J. G.; Renzoni, G. E.; Downing, J. W.; Michl, J.; Borden, W. T. J. Am. Chem. Soc. 1987, 109, 820. A bis-ethano derivative of n = O has been prepared: (f) Branan, B. M.; Paquette, L. A.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1992, 114, 774. Generation of a dimethyl derivative has also been reported: (g) Camps, P.; Font- Bardi, M.; Pérez, F.; Solans, X.; Vázquez, S. Angew. Chem., Int. Ed. Engl. 1995, 34, 912.
15. For n = 1, see: (a) Renzoni, G. E.; Yin, T.-K.; Borden, W. T. J. Am. Chem. Soc. 1986, 108, 7121. (b) Radziszewski, J. G.; Yin, T.-K.; Renzoni, G. E.; Hrovat, D. A.; Borden, W. T.; Michl, J. J. Am. Chem. Soc. 1993, 115, 1454. For n = 2, see: (c) Renzoni, G. E.; Yin, T.-K.; Miyake, F.; Borden, W. T. Tetrahedron 1986, 42, 1581. (d) Radziszewski, J. G.; Yin, T.-K.; Miyake, F.; Renzoni, G. E.; Borden, W. T.; Michl, J. J. Am. Chem. Soc. 1986, 108, 3544. (e) Yin, T.-K.; Radziszewski, J. G.; Renzoni, G. E.; Downing, J. W.; Michl, J.; Borden, W. T. J. Am. Chem. Soc. 1987, 109, 820. A bis-ethano derivative of n = O has been prepared: (f) Branan, B. M.; Paquette, L. A.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1992, 114, 774. Generation of a dimethyl derivative has also been reported: (g) Camps, P.; Font- Bardi, M.; Pérez, F.; Solans, X.; Vázquez, S. Angew. Chem., Int. Ed. Engl. 1995, 34, 912.
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50. RHF and Möller-Plesset calculations at the TCSCF-optimized geometries for 1 and 2 gave energies for the reaction in eq 1 that were 0.2-0.3 kcal/mol larger than those performed at the RHF-optimized geometries.
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59. Electron correlation must be included, in order to compute the energies of classical and nonclassical cations accurately. See, for example: Hehre, W. J.; Radom, L.; Schleyer, P. v. R.; Pople, J. A. Ab Initio Molecular Orbital Theory; Wiley-Interscience: New York, 1986; pp 379-396. Raghavachari, K.; Haddon, R. C.; Schleyer; P. v. R.; Schaefer, H. F., III. J. Am. Chem. Soc. 1983, 105, 5915. Yoshimine, M.; McLean, A. D.; Liu, B.; DeFrees, D. J.; Binkley, J. S. J. Am. Chem. Soc. 1983, 105, 6185. Schleyer, P. v. R.; Laidig, K.; Wiberg, K. B.; Saunders, M.; Schindler, M. J. Am. Chem. Soc. 1988, 110, 300. Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1990, 112, 3227.
60. Electron correlation must be included, in order to compute the energies of classical and nonclassical cations accurately. See, for example: Hehre, W. J.; Radom, L.; Schleyer, P. v. R.; Pople, J. A. Ab Initio Molecular Orbital Theory; Wiley-Interscience: New York, 1986; pp 379-396. Raghavachari, K.; Haddon, R. C.; Schleyer; P. v. R.; Schaefer, H. F., III. J. Am. Chem. Soc. 1983, 105, 5915. Yoshimine, M.; McLean, A. D.; Liu, B.; DeFrees, D. J.; Binkley, J. S. J. Am. Chem. Soc. 1983, 105, 6185. Schleyer, P. v. R.; Laidig, K.; Wiberg, K. B.; Saunders, M.; Schindler, M. J. Am. Chem. Soc. 1988, 110, 300. Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1990, 112, 3227.
61. Electron correlation must be included, in order to compute the energies of classical and nonclassical cations accurately. See, for example: Hehre, W. J.; Radom, L.; Schleyer, P. v. R.; Pople, J. A. Ab Initio Molecular Orbital Theory; Wiley-Interscience: New York, 1986; pp 379-396. Raghavachari, K.; Haddon, R. C.; Schleyer; P. v. R.; Schaefer, H. F., III. J. Am. Chem. Soc. 1983, 105, 5915. Yoshimine, M.; McLean, A. D.; Liu, B.; DeFrees, D. J.; Binkley, J. S. J. Am. Chem. Soc. 1983, 105, 6185. Schleyer, P. v. R.; Laidig, K.; Wiberg, K. B.; Saunders, M.; Schindler, M. J. Am. Chem. Soc. 1988, 110, 300. Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1990, 112, 3227.
62. Electron correlation must be included, in order to compute the energies of classical and nonclassical cations accurately. See, for example: Hehre, W. J.; Radom, L.; Schleyer, P. v. R.; Pople, J. A. Ab Initio Molecular Orbital Theory; Wiley-Interscience: New York, 1986; pp 379-396. Raghavachari, K.; Haddon, R. C.; Schleyer; P. v. R.; Schaefer, H. F., III. J. Am. Chem. Soc. 1983, 105, 5915. Yoshimine, M.; McLean, A. D.; Liu, B.; DeFrees, D. J.; Binkley, J. S. J. Am. Chem. Soc. 1983, 105, 6185. Schleyer, P. v. R.; Laidig, K.; Wiberg, K. B.; Saunders, M.; Schindler, M. J. Am. Chem. Soc. 1988, 110, 300. Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1990, 112, 3227.
63. Electron correlation must be included, in order to compute the energies of classical and nonclassical cations accurately. See, for example: Hehre, W. J.; Radom, L.; Schleyer, P. v. R.; Pople, J. A. Ab Initio Molecular Orbital Theory; Wiley-Interscience: New York, 1986; pp 379-396. Raghavachari, K.; Haddon, R. C.; Schleyer; P. v. R.; Schaefer, H. F., III. J. Am. Chem. Soc. 1983, 105, 5915. Yoshimine, M.; McLean, A. D.; Liu, B.; DeFrees, D. J.; Binkley, J. S. J. Am. Chem. Soc. 1983, 105, 6185. Schleyer, P. v. R.; Laidig, K.; Wiberg, K. B.; Saunders, M.; Schindler, M. J. Am. Chem. Soc. 1988, 110, 300. Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1990, 112, 3227.
64. 2 group in the cyclopropane ring of 5, was 2.8 kcal/mol higher than that of 6.
65. Smith, J. M.; Hrovat, D. A.; Borden, W. T. Tetrahedron Lett. 1993, 38, 5991.
66. 51 deprotonation of the resulting conformational isomer of 5 to give a conformational isomer of 6, followed by a second propano bridge flip to form 6. The RHF/6-31G* energies of the conformational isomers of 5 and 6 are respectively 8.0 and 5.9 kcal/mol higher than those of 5 and 6.