Reactivity of strained compounds: Is ground state destabilization the major cause for rate enhancement?

Journal of the American Chemical Society

Volumn 118, Issue 2, 1996, Pages 416-420

  Sella, Ariel ^a   Basch, Harold ^a   Hoz, Shmaryahu ^a  

^a BAR ILAN UNIVERSITY   (Israel)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000979520     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja951408c     Document Type: Article

References (26)

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2. Wiberg, K. B. Angew. Chem., Int. Ed. Engl. 1986, 25, 312.
3. Advances in Strain in Organic Chemistry; Halton, B., Ed.; JAI Press, London, 1991; Vol. 1.
4. See, for example: Wagner, H. U.; Szeimies, G.; Chandrasekhar, J.; Schleyer, P. v. R.; Pople, J. A.; Binkley, J. S. J. Am. Chem. Soc. 1978, 100, 1210. Dill, J. D.; Greenberg, A.; Liebman, J. F. J. Am. Chem. Soc. 1979, 101, 6814. Horvat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1988, 110, 4710.
5. See, for example: Wagner, H. U.; Szeimies, G.; Chandrasekhar, J.; Schleyer, P. v. R.; Pople, J. A.; Binkley, J. S. J. Am. Chem. Soc. 1978, 100, 1210. Dill, J. D.; Greenberg, A.; Liebman, J. F. J. Am. Chem. Soc. 1979, 101, 6814. Horvat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1988, 110, 4710.
6. See, for example: Wagner, H. U.; Szeimies, G.; Chandrasekhar, J.; Schleyer, P. v. R.; Pople, J. A.; Binkley, J. S. J. Am. Chem. Soc. 1978, 100, 1210. Dill, J. D.; Greenberg, A.; Liebman, J. F. J. Am. Chem. Soc. 1979, 101, 6814. Horvat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1988, 110, 4710.
7. Lawrence, C. D.; Tipper, C. F. H. J. Chem. Soc. 1955, 713. Skell, P. S.; Starer, I. J. Am. Chem. Soc. 1960, 82, 2971. Wiberg, K. B.; Kass, S. R. J. Am. Chem. Soc. 1985, 107, 1988.
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9. Lawrence, C. D.; Tipper, C. F. H. J. Chem. Soc. 1955, 713. Skell, P. S.; Starer, I. J. Am. Chem. Soc. 1960, 82, 2971. Wiberg, K. B.; Kass, S. R. J. Am. Chem. Soc. 1985, 107, 1988.
10. A referee pointed out that although this equation seems plausible, it contradicts the Hammond postulate (Hammond, G. S. J. Am. Chem. Soc. 1955, 77, 334). Namely, in a reaction where much strain energy is released, the Hammond postulate would predict an early TS. Yet, the earlier the TS, the less it will benefit from strain energy release. The latter will be more pronounced for a product like TS.
11. Lefller, J. E.; Grunwald, E. Rates and Equilibria of Organic Reactions; Wiley: New York, 1963.
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13. See, however, criticism of this approach: Hoz, S.; Basch, H.; Goldberg, M. J. Am. Chem. Soc. 1992, 114, 4364. Hoz. S. Acta Chem. Scand. 1992, 46, 503. Hoz, S. Acc. Chem. Res. 1993, 26, 69.
14. See, however, criticism of this approach: Hoz, S.; Basch, H.; Goldberg, M. J. Am. Chem. Soc. 1992, 114, 4364. Hoz. S. Acta Chem. Scand. 1992, 46, 503. Hoz, S. Acc. Chem. Res. 1993, 26, 69.
15. See, however, criticism of this approach: Hoz, S.; Basch, H.; Goldberg, M. J. Am. Chem. Soc. 1992, 114, 4364. Hoz. S. Acta Chem. Scand. 1992, 46, 503. Hoz, S. Acc. Chem. Res. 1993, 26, 69.
16. Chiang, Y.; Kresge, A. J.; Wiseman, J. R. J. Am. Chem. Soc. 1976, 98, 1564.
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18. Gaussian 92, Revision C, Frisch, M. J.; Trucks, G. W.; Head-Gordon, M.; Gill, P. M. W.; Wong, M. W.; Foresman, J. B.; Johnson, B. G.; Schlegel, H. B.; Robb, M. A.; Replogle, E. S., Gomperts, R.; Andres, J. L.; Raghavachari, K.; Binkley, J. S.; Gonzalez, C.; Martin, R. L.; Fox, D. J.; Defrees, D. J.; Baker, J.; Stewart, J. J. P.; and Pople, J. A.; Gassian, Inc.; Pittsburgh, PA, 1992.
19. Schleyer, P. v. R.; Williams, J. E.; Blanchard, K. R. J. Am. Chem. Soc. 1970, 92, 2377.
20. a = -0.7 kcal) reaction for the central bond cleavage. Substituting the MP2 values into eq 1, the amount of strain released at the TS is found to be 103%. This of course supports our conclusion even further. The results of these single point calculations are documented in the supporting information.
21. Wiberg, K. B.; Peters, K. S.; Ellison, G. B.; Alberti, F. J. Am. Chem. Soc. 1977, 99, 3946.
22. Pross, A.; Shaik, S. S. Acc. Chem. Res. 1983, 16, 363. Shaik, S. S. Progr. Phys. Org. Chem. 1985, 15, 197. Pross. A. Adv. Phys. Org. Chem. 1985, 15, 99. Ace. Chem. Res. 1985, 18, 212.
23. Pross, A.; Shaik, S. S. Acc. Chem. Res. 1983, 16, 363. Shaik, S. S. Progr. Phys. Org. Chem. 1985, 15, 197. Pross. A. Adv. Phys. Org. Chem. 1985, 15, 99. Ace. Chem. Res. 1985, 18, 212.
24. Pross, A.; Shaik, S. S. Acc. Chem. Res. 1983, 16, 363. Shaik, S. S. Progr. Phys. Org. Chem. 1985, 15, 197. Pross. A. Adv. Phys. Org. Chem. 1985, 15, 99. Ace. Chem. Res. 1985, 18, 212.
25. Pross, A.; Shaik, S. S. Acc. Chem. Res. 1983, 16, 363. Shaik, S. S. Progr. Phys. Org. Chem. 1985, 15, 197. Pross. A. Adv. Phys. Org. Chem. 1985, 15, 99. Ace. Chem. Res. 1985, 18, 212.
26. Hoz, S. In The Chemistry of the Cyclopropyl Group; Rappoport, Z., Ed.; Wiley: New York, 1987; Chapter 19.