Understanding the participation of 3-nitropyridine in polar Diels-Alder reactions. A DFT study

作者：Ormachea Carla M; Mancini Pedro M E^*; Kneeteman Maria N; Domingo Luis R

来源：Computational and Theoretical Chemistry, 2015, 1072: 37-42.

DOI：10.1016/j.comptc.2015.08.024

• 3-Nitropyridine
• Polar Diels-Alder
• Molecular mechanisms
• Regioselectivity
• DFT indices
• Parr functions

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.

• 出版日期2015-11-15