TY - JOUR
T1 - Computational investigation of 1,3-H and 1,5-H shifts in isomerization of enol acetate of 2-aceto-1,3-cyclohexanedione
AU - Wang, Yanhua
AU - Chen, Xuesong
AU - Li, Li
AU - Zou, Jianwei
PY - 2009/6
Y1 - 2009/6
N2 - The mechanism of the isomerization of the enol acetate of 2-aceto-1,3-cyclohexanedione has been discussed in detail. The possible 1,3-H and 1,5-H shifts in isomerization were investigated systematically. It seems that this mechanism includes two successive 1,5-sigmatropic shifts, i.e. 1,5-acetyl and 1,5-H shifts. Density functional theory calculations have been performed to evaluate the reasonability of the proposed mechanisms. The effect of the solvent upon the rate-determining steps has been also considered. In addition, the relative stabilities of the reactant, the product as well as the intermediates in the proposed mechanism have been examined and discussed.
AB - The mechanism of the isomerization of the enol acetate of 2-aceto-1,3-cyclohexanedione has been discussed in detail. The possible 1,3-H and 1,5-H shifts in isomerization were investigated systematically. It seems that this mechanism includes two successive 1,5-sigmatropic shifts, i.e. 1,5-acetyl and 1,5-H shifts. Density functional theory calculations have been performed to evaluate the reasonability of the proposed mechanisms. The effect of the solvent upon the rate-determining steps has been also considered. In addition, the relative stabilities of the reactant, the product as well as the intermediates in the proposed mechanism have been examined and discussed.
KW - 2-aceto-1,3-cyclohexanedione
KW - Density functional theory
KW - Hydrogen shift
KW - Isomerization mechanism
KW - Solvent effect
UR - http://www.scopus.com/inward/record.url?scp=67651167059&partnerID=8YFLogxK
U2 - 10.1002/cjoc.200990189
DO - 10.1002/cjoc.200990189
M3 - Article
AN - SCOPUS:67651167059
SN - 1001-604X
VL - 27
SP - 1132
EP - 1136
JO - Chinese Journal of Chemistry
JF - Chinese Journal of Chemistry
IS - 6
ER -