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Computational Investigation of 1,3‐H and 1,5‐H Shifts in Isomerization of Enol Acetate of 2‐Aceto‐1,3‐cyclohexanedione
Author(s) -
WANG Yanhua,
CHEN Xuesong,
LI Li,
ZOU Jianwei
Publication year - 2009
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.200990189
Subject(s) - chemistry , isomerization , enol , mechanism (biology) , computational chemistry , density functional theory , sigmatropic reaction , reaction mechanism , keto–enol tautomerism , solvent , photochemistry , medicinal chemistry , organic chemistry , tautomer , catalysis , philosophy , epistemology
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.