Understanding the molecular mechanism of γ‐elimination of nitrous acid in the framework of the molecular electron density theory

Abstract

The reactions of γ-dehydronitration of furaxanenitrolic acids have been studied within the density functional theory using molecular electron density theory scheme at the MPWB1K(PCM)/6-311G(d,p) level of theory. The alteration of bonding along the course of the reaction is studied in the topology of the electron density functional within the bonding evolution theory perspective. The characteristics of electron density changes indicate that we can distinguish six different phases in the nitrous acid extrusion from furaxanenitrolic acid 1a. These different phases related to the intrinsic reaction coordinate path of the analyzed reaction denote the nonconcerted nature of the molecular mechanism.

Mechanistic aspects of the synthesis of seven‐membered internal nitronates via stepwise [4 + 3] cycloaddition involving conjugated nitroalkenes: Molecular Electron Density Theory computational study

“…For comparison, the C3-O4 interatomic distance at this level is longer than 3.8 Å. This distance exists beyond the typical range for this type of bonds; within transition states 44,50,51 TS1a exhibits evidently polar nature. This is confirmed by the high GEDT value (0.61 e).…”

Understanding the Regioselectivity and the Molecular Mechanism of [3 + 2] Cycloaddition Reactions between Nitrous Oxide and Conjugated Nitroalkenes: A DFT Computational Study

“…The introduction of nitro groups for these types of molecules increases the potential activity of the considered molecules [ 4 ]. Additionally, the nitro group opens a wide range of possibilities for the further functionalization of amines [ 5 ], nitrile N-oxides [ 6 ], oximes [ 7 ], nitronic esters [ 8 ], and many others [ 9 ]. Thus, the question of the preparation of nitro-functionalized five-membered heterocycles has attracted the attention of many researchers around the world.…”