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MECHANISMS FOR THE FORMATION OF FIVE-MEMBERED RINGS IN ETHENE ADDITION REACTIONS WITH AZOMETHINE YLIDE AND ALLYL ANION

Михаил E. Клецкий, Олег Н. Буров, Никита C. Федик, Сергей B. Курбатов
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Abstract


The mechanisms of pyrrolidine and cyclopentyl anion formation from ethene and allyl anion, azomethine ylide, as well as their electron-rich and electron-poor derivatives was studied for a wide range of systems by ab initio calculations using the MP2/6-311++G(d,p) basis set. The calculations showed that during the interaction of allyl anion with ethene the five-center intermediate species with CS symmetry was stabilized by direct electron donation effect, while in the case of azomethine ylide it was simultaneously affected by direct and reverse donation mechanisms. The introduction of electron-withdrawing substituents at the central position of allyl anion enabled a concerted synchronous cycloaddition process, while the reaction proceeded by single-step mechanism in the case of azomethine ylide having electron-donating or electron-withdrawing substituents at the nitrogen atom, except with sterically congested reactants.

Authors: Mikhail E. Kletskii*, Oleg N. Burov, Nikita S. Fedik, Sergey V. Kurbatov

 


Keywords


allyl anion; azomethine ylide; cyclopentyl anion; pyrrolidine; ab initio calculations; cycloaddition; MP2 perturbation theory

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