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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.
Abstract:
N-Aryl ketenimines have been established as highly reactive aza-dienophiles. Intermolecular cycloadditions are achieved upon heating in the presence of 2,5-bis(silyloxy)furans and proceed with high levels of peri-, regio-, chemo- and diastereo-selectivity. Spontaneous C-O cleavage yields oxygenated pyridone derivatives in a highly convergent and redox-neutral manner. Combined experimental and computational studies demonstrate N-aryl ketenimines to be significantly more reactive than imino dienophiles, as a consequence of less distorted transition states. Derivatization studies include the development of isocyanate and cyclic ketenimine equivalents as aza-dienophiles, while extension to a one-pot aza-Diels-Alder/oxa-Diels-Alder sequence provides a three-component approach to complex fused pyridone/pyran systems.
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