Atomic motions and protonation stereochemistry in nucleophilic additions to bicyclobutanes

Journal of the American Chemical Society

Volumn 118, Issue 23, 1996, Pages 5456-5461

  Hoz, Shmaryahu ^a   Azran, Carmela ^a   Sella, Ariel ^a  

^a BAR ILAN UNIVERSITY   (Israel)

Author keywords

[No Author keywords available]

Indexed keywords

CYCLOBUTANE DERIVATIVE;

ARTICLE; DRUG STRUCTURE; MOLECULAR DYNAMICS;

EID: 0029904367     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja960370g     Document Type: Article

References (28)

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7. Bell, R. P. In The Proton In Chemistry; Chapman and Hall: London, 1973; Chapter 10. Bordwell, F. G.; Bares, J. E.; Bartmess, J. E.; Drucker, G. E.; Gerhold, J.; McCollum, G. J.; Van Der Puy, M.; Vanier, N. R.; Matthews, W. S. J. Org. Chem. 1977, 42, 326. Fujio, M.; McIver, R. T., Jr.; Taft, R. W. J. Am. Chem. Soc. 1981, 103, 4017. Hibbert, F. In The Chemistry of Functional Groups, Supplement C; Patai, S., Ed.; Wiley: New York, 1982; Chapter 17. Lien, M. H.; Hopkinson, A. C.; McKinney, M. A. J. Mol. Struct. Theochem. 1983, 105, 37. Delbeck, F. J. Org. Chem. 1984, 49, 4838. Abbotto, A.; Bradamante, S.; Pagani, G. A. J. Org. Chem. 1993, 58, 444, 449.
8. Bell, R. P. In The Proton In Chemistry; Chapman and Hall: London, 1973; Chapter 10. Bordwell, F. G.; Bares, J. E.; Bartmess, J. E.; Drucker, G. E.; Gerhold, J.; McCollum, G. J.; Van Der Puy, M.; Vanier, N. R.; Matthews, W. S. J. Org. Chem. 1977, 42, 326. Fujio, M.; McIver, R. T., Jr.; Taft, R. W. J. Am. Chem. Soc. 1981, 103, 4017. Hibbert, F. In The Chemistry of Functional Groups, Supplement C; Patai, S., Ed.; Wiley: New York, 1982; Chapter 17. Lien, M. H.; Hopkinson, A. C.; McKinney, M. A. J. Mol. Struct. Theochem. 1983, 105, 37. Delbeck, F. J. Org. Chem. 1984, 49, 4838. Abbotto, A.; Bradamante, S.; Pagani, G. A. J. Org. Chem. 1993, 58, 444, 449.
9. Bell, R. P. In The Proton In Chemistry; Chapman and Hall: London, 1973; Chapter 10. Bordwell, F. G.; Bares, J. E.; Bartmess, J. E.; Drucker, G. E.; Gerhold, J.; McCollum, G. J.; Van Der Puy, M.; Vanier, N. R.; Matthews, W. S. J. Org. Chem. 1977, 42, 326. Fujio, M.; McIver, R. T., Jr.; Taft, R. W. J. Am. Chem. Soc. 1981, 103, 4017. Hibbert, F. In The Chemistry of Functional Groups, Supplement C; Patai, S., Ed.; Wiley: New York, 1982; Chapter 17. Lien, M. H.; Hopkinson, A. C.; McKinney, M. A. J. Mol. Struct. Theochem. 1983, 105, 37. Delbeck, F. J. Org. Chem. 1984, 49, 4838. Abbotto, A.; Bradamante, S.; Pagani, G. A. J. Org. Chem. 1993, 58, 444, 449.
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12. In nucleophilic attacks on bicyclobutane, the nucleophile always approaches the molecule from the equatorial direction. For a review of the chemistry of bicyclobutane, see: Hoz, S. In The Chemistry of the Cyclopropyl Group; Rappoport, Z., Ed.; Wiley: New York, 1987; Chapter 19.
13. In 1,3-disubstituted cyclobutane, cis substitution is more stable, since the two bulky substituents can simultaneously adopt the cis diequatorial geometry. Moriarty, R. M. Top. Stereochem, 1974, 8, 271.
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15. The hydrogens on the 1 and 3 carbons are shifted to lower fields when they are cis to an electronegative groups. Hoz, S.; Livneh, M.; Cohen, D. J. Org. Chem. 1986, 51, 4537 (see also ref 16 below and references cited therein).
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19. Hoz, S.; Basch, H.; Goldberg, M.; J. Am. Chem. Soc. 1992, 114, 4364.
20. A referee had suggested an alternative explanation for the observed stereochemistry at high proton donor concentration. According to this explanation, at high MeOH concentration, the reaction is concerted, and no free carbanion is formed under these conditions. We believe that this suggestion can be safely ruled out on the basis of microscopic reversibility since all the 1,3-elimination reactions in the cyclobutane bicyclobutane system are known to be stepwise (see ref 6 above). Moreover, to the best of our knowledge, there is no single reported case of a concerted 1,3-elimination reaction. The reversal must therefore also be a stepwise reaction.
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26. Blanchard E. P.; Cairncross, A. J. Am. Chem. Soc. 1966, 88, 487. Hall, H. K., Jr.; Blanchard, E. P. Jr.; Cherkofsky, C. S.; Sieja, J. B. J. Am. Chem. Soc. 1971, 93, 110. Dietz, P.; Szeimies, G. Chem. Ber. 1980, 113, 398. Hall, H. K., Jr.; Smith, C. D.; Blanchard, E. P., Jr.; Cherkofsky, C. S.; Sieja, J. B. J. Am. Chem. Soc. 1971, 93, 121.
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