Exploring the Regioselectivity of Diels–Alder Reactions of 2,6-Disubstituted Benzoquinones through DFT Calculations

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Publikace nespadá pod Ústav výpočetní techniky, ale pod Přírodovědeckou fakultu. Oficiální stránka publikace je na webu muni.cz.
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KALLA Erik SEMRÁD Hugo MAIER Lukáš PARUCH Kamil ZIPSE Hendrik MUNZAROVÁ Markéta

Rok publikování 2025
Druh Článek v odborném periodiku
Časopis / Zdroj European Journal of Organic Chemistry
Fakulta / Pracoviště MU

Přírodovědecká fakulta

Citace
www https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejoc.202500661
Doi https://doi.org/10.1002/ejoc.202500661
Klíčová slova computational chemistry; Diels–Alder reaction; dienes; dienophiles; substituted benzoquinones
Přiložené soubory
Popis Diels–Alder reactions of 2-methyl-6-substituted-p-benzoquinones are studied using quantum chemical calculations. The effect of 19 substituents, including halomethyl, alkyl, vinyl, ethynyl, nitrile, trifluoromethyl, methoxy, cyclohexenyl, phenyl, and trifluoromethoxyphenyl groups, on the reaction barriers is explored by the B3LYP-D3, M06-2X, and DLPNO-CCSD(T) methods. Gibbs free activation energies are compared for the two regioisomeric products experimentally observed in the reaction mixture. For 75% of the substituents, the calculated barrier difference (?G‡b – ?G‡a) lies within 2.0?kcal?mol-1 of the value determined from the experimentally observed product ratio a/b. Activation barriers are further analyzed in terms of the underlying deformation and interaction energies. The difference in deformation energies of transition states corresponding to the two regioisomers ranges from -8.0 to +8.0?kcal?mol-1 and is directly proportional to experimental ln(a/b) values. Differences in interaction energies between regioisomeric transition states are, in comparison, significantly smaller.
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