DFT investigation of Diels-Alder reaction of ethyl propiolate to cage-annulated hexacyclo[,6.06,13.08,12.010,14]hexadeca-2,4-diene-7,16-dione

Abdurrahman Atalay, Riza Abbasoglu


The Diels-Alder (DA) reaction between cage-annulated diene hexacyclo[,6.06,13.08,12.010,14]hexadeca-2,4-diene-7,16-dione (HHDD) with cyclohexa-1,3-diene moiety and ethyl propiolate (EP) dienophile were investigated by DFT method at B3LYP/6-31+G(d,p) level to elucidate mechanism and regioselectivity features of the reaction. The geometrical and electronic structures of caged diene HHDD and EP were studied at B3LYP/6-31+G(d,p) level. In order to identify facial- and regio-selectivity of the DA reaction of HHDD and EP, frontier molecular orbital (FMO) interactions of reactants according to FMO theory, and molecular electrostatic potential map of HHDD were examined. Potential energy surface (PES) of the related DA reaction was calculated, and optimizations of transition states and of products corresponding to critical points on PES were performed at B3LYP/6-31+G(d,p), and their configurations were determined. In addition, thermodynamic and kinetic parameters of each possible cycloaddition reaction were calculated using B3LYP/6-31+G(d,p)  method to find out that the reaction takes place under thermodynamic or kinetic control. The thermochemical results showed that the  related DA cycloaddition proceed under kinetic kontrol, and activation energies of syn cycloadditions are clearly lower than that of anti cycloadditions. The theoretical calculations are in good agreement with experimental results.


DFT calculations; Diels-Alder cycloadditions; cage-fused dienes; π-facial selectivity

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DOI: https://doi.org/10.2298/JSC171113035A

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