Push-pull nitronates in the [3+2] cycloaddition with nitroethylene: Molecular Electron Density Theory study
1Institute of Organic Chemistry and Technology, Cracow University of Technology, Warszawska 24, 31-155, Cracow, Poland.
Abstract:
The structure and the participation of the N-methoxy-N-[bis(methoxycarbonyl)methylene]amine N-oxide as model push-pull nitronate 1 with nitroethylene 2 in [3 + 2] cycloaddition (32CA) reaction have been analyzed within the Molecular Electron Density Theory (MEDT) using Density Functional Theory (DFT) calculations at the B3LYP(PCM)/6-31G(d) level. Topological analysis of the Electron Localization Function (ELF) of nitronate 1 reveals that this compound has pseudoradical center, while the conceptual DFT reactivity indices characterizes this three-atom-component (TAC) as a strong electrophile. The analyzed 32CA reaction takes place through a one-step mechanism. A Bonding Evolution Theory (BET) study of the more favorable reaction path associated with the 32CA reaction of nitronate 1 with nitroethylene 2 indicates that it is associated with a non-concerted two-stage one-step mechanism, in which the activation energy is mainly related with to the initial formation of the O3-C4 single bond. In the case of this reaction, an additional mechanism with formation of intermediate 7 is also found.
Related Concept Videos
Nitrosation of Enols
Cycloaddition Reactions: Overview
Nucleophilic Addition to the Carbonyl Group: General Mechanism
A stronger nucleophile can directly attack the electrophilic center, the carbonyl carbon. The HOMO orbital of the nucleophile interacts with the LUMO (π* antibonding) orbital present on the carbonyl carbon. This interaction breaks the π bond and shifts the π...
Cycloaddition Reactions: MO Requirements for Thermal Activation
meta-Directing Deactivators: –NO2, –CN, –CHO, –⁠CO2R, –COR, –CO2H
1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism

![Solid-phase Synthesis of [4.4] Spirocyclic Oximes](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F58508.jpg&w=3840&q=50)
