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Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
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Electrophilic Intermediates in the Nef and Meyer Reactions: A Computational Study
Roman S Malykhin1, Alexey Yu Sukhorukov1
1Laboratory of organic and metal-organic nitrogen-oxygen systems, N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky prospect, 47, Moscow 119991, Russian Federation.
The Journal of Organic Chemistry
|December 7, 2024
Summary
Quantum-chemical calculations reveal new details on nitroalkane activation via the Nef and Meyer reactions. New electrophilic species, N-oxoiminium and N-hydroxynitrilium cations, are identified as key intermediates, expanding reaction possibilities.
Area of Science:
- Organic Chemistry
- Computational Chemistry
- Reaction Mechanisms
Background:
- The Nef and Meyer reactions involve the activation of nitroalkanes with protic acids.
- Understanding the intermediate electrophilic species is crucial for elucidating reaction mechanisms.
Purpose of the Study:
- To investigate the generation, interconversion, and reactivity of electrophilic species in nitroalkane activation.
- To elucidate the mechanisms of the Nef and Meyer reactions using computational methods.
Main Methods:
- Quantum-chemical calculations were employed to study reaction pathways.
- Analysis of intermediate species including N,N-Bis(hydroxy)iminium, N-oxoiminium, and N-hydroxynitrilium cations.
Main Results:
- N-oxoiminium and N-hydroxynitrilium cations are formed independently from aci-nitroalkanes and via C-H bond cleavage, respectively.
- These cations are potent electrophiles, reacting with unactivated arenes.
- N-oxoiminium cations exhibit unusual ambident reactivity with three electrophilic centers.
Conclusions:
- Computational findings illuminate key mechanistic aspects of the Nef and Meyer reactions.
- The study predicts the potential for numerous interrupted versions of these reactions.
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