A theoretical study on the regio- and stereoselectivity of [3+2] cycloddition of β-trifluoroacetyl vinyl ethyl ether with 3-oxo-1,2-pyrazolidinium ylides

Mina haghdadi, Nasim Nab

Abstract


[3+2] cycloaddition reactions of β-trifluoroacetyl vinyl ethyl ether (1) with substituted and unsubstitued 3-oxo-1,2-pyrazolidinium ylides (2a-2e) were studied by using density functional theory (DFT) methods at the cc-pVDZ level. The mechanistic details of these reactions, especially with respect to regio- and stereoselectivity, were analyzed. Analysis of the relative energies which were associated with the different reaction pathways indicates the presence of the trifluoroacetyl group in the dipolarophile and substituents on the aryl ring in the dipolar have a remarkable effect on selectivity. Also, it is found that the ortho-endo pathway with the lowest activation energy is preferred, which is in good agreement with the experimental data. Moreover, the elimination of ethanol from [3+2] cycloadducts and the formation of bicyclic pyrazolidinones are explained in order to give a total description of the complete domino processes. The inclusion of solvent effects increases the activation energies and the exothermic character of cycloadducts, but does not change the gas phase selectivity. DFT-based reactivity indices clearly predict the experimental regiochemistry.


Keywords


DFT study; trifluoroacetyl group; 3-oxopyrazolidin-2-ium-1-ide; reactivity indices; cycloaddition reaction; bicyclic pyrazolidinone

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DOI: http://dx.doi.org/10.2298/JSC170511099H

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