Understanding the participation of 3-nitropyridine in polar Diels-Alder reactions. A DFT study
The reactivity of 3-nitropyridine acting as an electrophilic dienophile in polar Diels-Alder (P-DA) reactions toward three different dienes of increased nucleophilicity has been theoretically studied using DFT methods at the MPWB1K/6-31G(d) level. It has been observed that this aromatic heterocyclic...
| Autores: | , , , |
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| Tipo de documento: | artigo |
| Estado: | Versão publicada |
| Data de publicação: | 2015 |
| País: | Argentina |
| Recursos: | Consejo Nacional de Investigaciones Científicas y Técnicas |
| Repositório: | CONICET Digital (CONICET) |
| Idioma: | inglês |
| OAI Identifier: | oai:ri.conicet.gov.ar:11336/84957 |
| Acesso em linha: | http://hdl.handle.net/11336/84957 |
| Access Level: | Acceso aberto |
| Palavra-chave: | 3-NITROPYRIDINE DFT INDICES MOLECULAR MECHANISMS PARR FUNCTIONS POLAR DIELS-ALDER REGIOSELECTIVITY https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
| Resumo: | The reactivity of 3-nitropyridine acting as an electrophilic dienophile in polar Diels-Alder (P-DA) reactions toward three different dienes of increased nucleophilicity has been theoretically studied using DFT methods at the MPWB1K/6-31G(d) level. It has been observed that this aromatic heterocyclic system suffers cycloaddition reactions yielding isoquinoline derivatives. The present DFT study establishes that while the P-DA reactions with isoprene and 1-methoxy-1,3-butadiene take place through a two-stage one-step mechanism, the use of the strong nucleophilic Danishefsky's diene changes the mechanism to a two-step one with formation of a zwitterionic intermediate. These P-DA reactions are completely regioselective allowing the formation of a unique substituted isoquinoline. Analysis of the DFT reactivity indices at the ground state of the reagents correctly explains the reactivity and regioselectivity for these P-DA reactions. |
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