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

Authors

  • Михаил E. Клецкий Southern Federal University, 7 Zorge St., Rostov-on-Don 344090
  • Олег Н. Буров Southern Federal University, 7 Zorge St., Rostov-on-Don 344090
  • Никита C. Федик Southern Federal University, 7 Zorge St., Rostov-on-Don 344090
  • Сергей B. Курбатов Southern Federal University, 7 Zorge St., Rostov-on-Don 344090

DOI:

https://doi.org/10.1007/3301

Keywords:

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

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

 

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Published

2016-09-30

Issue

Vol. 52 No. 9 (2016): Pericyclic reactions in heterocyclic chemistry

Section

Original Papers