Negative Ion Hyperconjugation and Its Relevance to the Mechanism of E1cB Reactions. An ab Initio Study

Journal of Organic Chemistry

Volumn 62, Issue 2, 1997, Pages 244-245

  Saunders Jr , William H ^a  

^a UNIVERSITY OF ROCHESTER   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000780879     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9611778     Document Type: Article

References (13)

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3. Hoffmann, R.; Radom, L.; Pople, J. A.; Schleyer, P. v. R.; Hehre, W. J.; Salem, S. J. Am. Chem. Soc. 1972. 94, 6221-6223.
4. Holtz, D.; Streitwieser, A.; Jesaitis, R. G. Tetrahedron Lett. 1969, 4529-4532.
5. Farnham, W. B.; Smart, B. E.; Middleton, W. J.; Calabrese, J. C.; Dixon, D. A. J. Am. Chem. Soc. 1985, 107, 4565-4567.
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7. Schleyer, P. v. R.; Kos, A. J. Tetrahedron 1983, 39, 1141-1150.
8. Apeloig, Y. J. Chem. Soc., Chem. Commun. 1981, 396-398.
9. A reviewer questions the reality of 6 in view of the small barrier. The potential energy barrier is 3.9 kcal and the imaginary frequency is 1187i, so there seems no room for doubt that it represents a real saddle point.
10. Matsson, O.; Persson, J.; Axelsson, B. S.; Långstrom, B. J. Am. Chem. Soc. 1993, 115, 5288-5289.
11. Persson, J.; Axelsson, S.; Matsson, O. J. Am. Chem. Soc. 1996, 118, 20-23.
12. Calculated KIE's in E2 reactions of ethyl chloride with various bases have been reported: Glad, S. S.; Jensen, F. J. Am. Chem. Soc. 1994, 116, 9302-9310.
13. Gandler, J. R.; Jencks, W. P. J. Am. Chem. Soc. 1982, 104, 1937-1951.