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Updated: May 29, 2025

Preparation of Stable Bicyclic Aziridinium Ions and Their Ring-Opening for the Synthesis of Azaheterocycles
Published on: August 22, 2018
Ketenimines as Aza-Dienophiles
Christopher J DeAngelis1, Geeta Goyal1, Marshall J Liss1
1Department of Chemistry, University of Georgia, Athens, Georgia 30602, United States.
N-Aryl ketenimines serve as potent aza-dienophiles, enabling selective cycloadditions with furan derivatives. This reaction efficiently produces oxygenated pyridones through a convergent, redox-neutral pathway.
Area of Science:
- Organic Chemistry
- Synthetic Chemistry
Background:
- N-Aryl ketenimines are known for their reactivity.
- Aza-dienophiles are crucial in cycloaddition reactions.
Purpose of the Study:
- To explore the cycloaddition reactions of N-Aryl ketenimines.
- To develop a method for synthesizing oxygenated pyridone derivatives.
- To investigate the reactivity of N-Aryl ketenimines compared to other dienophiles.
Main Methods:
- Intermolecular cycloadditions using N-Aryl ketenimines and 2,5-bis(silyloxy)furans.
- Heating reactions in the presence of catalysts.
- Experimental and computational studies.
- Derivatization of aza-dienophiles.
- One-pot multi-component reactions.
Main Results:
- High levels of peri-, regio-, chemo-, and diastereoselectivity were achieved.
- Spontaneous C-O cleavage led to oxygenated pyridone derivatives.
- N-Aryl ketenimines showed higher reactivity than imino dienophiles due to less distorted transition states.
- Development of isocyanate and cyclic ketenimine equivalents.
- A three-component approach to fused pyridone/pyran systems was established.
Conclusions:
- N-Aryl ketenimines are highly effective aza-dienophiles for synthesizing oxygenated pyridones.
- The reaction pathway is convergent and redox-neutral.
- The enhanced reactivity of N-Aryl ketenimines offers advantages in synthetic strategies.
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