A DFT investigation of the Diels–Alder reaction of ethyl propiolate to the cage-annulated hexacyclo[7.5.2.01,6.06,13.08,12.010,14]hexadeca-2,4-diene-7,16-dione

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Abdurrahman Atalay
Riza Abbasoglu

Abstract

The Diels–Alder (DA) reaction between the cage-annulated diene hexacyclo[7.5.2.01,6.06,13.08,12.010,14]hexadeca-2,4-diene-7,16-dione (HHDD) with a cyclohexa-1,3-diene moiety and ethyl propiolate (EP) dienophile was investigated by the DFT method at the B3LYP/6-31+G(d,p) level to elucidate the mechanism and regioselectivity features of the reaction. The geometrical and electronic structures of the 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, the frontier molecular orbital (FMO) inter­actions of the reactants according to the FMO theory, and the molecular elec­tro­static potential map of HHDD were examined. The potential energy surface (PES) of the related DA reaction was calculated, and optimizations of trans­ition states and of products corresponding to critical points on the PES were performed at the B3LYP/6-31+G(d,p), and their configurations were deter­mined. In addition, the thermodynamic and kinetic parameters of each possible cycloaddition reaction were calculated using the B3LYP/6-31+G(d,p) method to determine whether the reaction occurs under thermodynamic or kinetic con­trol. The thermochemical results showed that the related DA cycloaddition pro­ceeds under kinetic control, and the activation energies of syn cycloadditions are clearly lower than that of anti cycloadditions. The theoretical calculations are in good agreement with experimental results.

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How to Cite
[1]
A. Atalay and R. Abbasoglu, “A DFT investigation of the Diels–Alder reaction of ethyl propiolate to the cage-annulated hexacyclo[7.5.2.01,6.06,13.08,12.010,14]hexadeca-2,4-diene-7,16-dione”, J. Serb. Chem. Soc., vol. 83, no. 7-8, pp. 837–846, Aug. 2018.
Section
Theoretical Chemistry

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