Stereoelectronic, torsional, and steric effects on rates of enolization of ketones

被引:23
作者
Behnam, SM [1 ]
Behnam, SE
Ando, K
Green, NS
Houk, KN
机构
[1] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA
[2] Univ Ryukyus, Coll Educ, Nishihara, Okinawa 9030213, Japan
关键词
D O I
10.1021/jo000905v
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
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.
引用
收藏
页码:8970 / 8978
页数:9
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