From Chemistry Towards Technology Step-By-Step From Chemistry Towards Technology Step-By-Step От химии к технологии шаг за шагом 2782-1900 82569 10.52957/27821900_2021_03_56 Научные статьи Scientific articles Научные статьи Quantum-chemical study of the regioselectivity of the diels-alder heteroreaction of α,β-unsaturated thiocarbonyl compounds with unsymmetrical dienophiles Квантово-химическое изучение региоселективности гетерореакции Дильса-Альдера α,β-непредельных тиокарбонильных соединений с несимметричными диенофилами Овчинников Константин Львович Ovchinnikov Konstantin L'vovich

кандидат химических наук;

candidate of chemical sciences;

 Старостин Михаил Витальевич Starostin Mihail Vital'evich Ларионов Николай Николаевич Larionov Nikolay Nikolaevich Ярославский государственный технический университет Yaroslavl State Technical University 23 09 2021 23 09 2021 2 3 56 60 20 09 2021 06 09 2021 https://chemintech.ru/en/nauka/article/82569/view

Выполнено квантово-химическое исследование гетерореакции Дильса-Альдера получения различных замещенных 3,4 дигидро-2H-тиопиранов. Исследованы стерический и электронный факторы, влияющие на протекание реакции α,β-непредельных тиокарбонильных соединений с несимметричными диенофилами. Использованы методы AM1, B3LYP. В результате анализа расчетных данных для случая несимметричных диенофилов было доказано, что региоселективность реакции подчиняется электронному фактору и может быть описана энергиями активации реакции, энергиями и параметрами локализации граничных орбиталей. Расчетные данные подтверждаются экспериментальными.

The study considers the quantum-chemical study of the Diels-Alder heteroreaction of various substituted 3,4-dihydro-2H-thiopyrans. We study the steric and electronic factors influencing the reaction of α,β-unsaturated thiocarbonyl compounds with unsymmetrical dienophiles. We used the methods AM1, B3LYP. The analysis of calculated data for asymmetric dienophiles shows that the regioselectivity of the reaction is subject to the electron factor and can be described by the reaction activation energies, energies and localisation parameters of the boundary orbitals. The calculations are confirmed by the experimental results.

 непредельные тиокарбонильные соединения гетерореакция Дильса-Альдера тиопираны квантово-химическое моделирование теория функционала плотности unsaturated thiocarbonyl compounds Diels-Alder heteroreaction thiopyrans quantum-chemical modelling density functional theory

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