Study of the effect of substituents and temperature on the regio- and stereoselectivity of diene condensation of 1-alkyl-substituted dienes with alkyl acrylates
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In reactions of diene condensation of 1-alkyl-substituted dienes with alkyl acrylates, an increase in the radical in the acrylate causes a decrease in the proportion of ortho- and cis-isomers due to steric factors.
An increase in the radical in the diene does not result in a decrease in the proportion of ortho isomers: the change in both the regio- and the stereoselectivity is small and irregular in this case. At the same time, the change in the enthalpies and entropies of selectivity is regular; a compensation effect is observed, and a change in the enthalpies of selectivity favors an increase in the proportion of meta- and cis-isomers.
The factors which affect the activation parameters of selectivity were examined. A conclusion was drawn concerning the nonequivalence of the bonds formed in the transition state and movement of the latter along the reaction coordinate toward the adduct with an increase in the radical in the diene.
KeywordsEntropy Enthalpy Adduct Transition State Diene
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