Stereoelectronic, Torsional, and Steric Effects on Rates of Enolization of Ketones

The stereoselectivities of base-catalyzed enolizations of ketones have been studied by quantum mechanical methods. Transition structures of exo and endo deprotonation of camphor, norcamphor, and dehydronorcamphor have been located with two model bases. Stereoelectronic, torsional, and steric effects...

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Bibliographic Details
Published in:Journal of organic chemistry 2000-12, Vol.65 (26), p.8970-8978
Main Authors: Behnam, Shahrad M, Behnam, Shahdad E, Ando, Kaori, Green, Nora S, Houk, K. N
Format: Article
Language:English
Subjects:
Catalysis
Ketones - chemistry
Models, Molecular
Molecular Conformation
Molecular Structure
Stereoisomerism
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Summary:The stereoselectivities of base-catalyzed enolizations of ketones have been studied by quantum mechanical methods. Transition structures of exo and endo deprotonation of camphor, norcamphor, and dehydronorcamphor have been located with two model bases. Stereoelectronic, torsional, and steric effects on activation energies were assessed. These calculations demonstrate the importance of torsional strain between partial bonds and vicinal bonds on the rates of deprotonation and on related reactions involving the formation of enolates or reactions of enols and enolates.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo000905v