On the Question of the Course of the Hetero Diels–Alder Reactions Between <i>N</i>-(2,2,2-Trichloroethylidene)Carboxamides and Dicyclohexylcarbodiimide: A New Case of the Stepwise Zwitterionic Cycloaddition Process

The regioselectivity and the molecular mechanism of the Diels–Alder reactions between <i>N</i>-(2,2,2-trichloroethylidene)carboxamides and dicyclohexylcarbodiimide were explored based on the ωB97xd/6-311G(d) (PCM) calculations. It was found that the reaction course is determined by polar...

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Main Authors: Przemysław Woliński, Karolina Zawadzińska-Wrochniak, Ewa Dresler, Radomir Jasiński
Format: Article
Language:English
Published: MDPI AG 2025-06-01
Series:Molecules
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Online Access:https://www.mdpi.com/1420-3049/30/13/2692
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Summary:The regioselectivity and the molecular mechanism of the Diels–Alder reactions between <i>N</i>-(2,2,2-trichloroethylidene)carboxamides and dicyclohexylcarbodiimide were explored based on the ωB97xd/6-311G(d) (PCM) calculations. It was found that the reaction course is determined by polar local interactions. It is interesting that the most favored reaction channel is realized not via classical single-step Diels–Alder mechanism, but according to the stepwise scheme with the intervention of the zwitterionic intermediate. The details of the electron density redistribution along the reaction coordinate were explained using the ELF technique.
ISSN:1420-3049