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Updated: Jan 13, 2026

Preparation of Stable Bicyclic Aziridinium Ions and Their Ring-Opening for the Synthesis of Azaheterocycles
Published on: August 22, 2018
Generation of Mono- and Bisazabicyclic o-Quinodimethanes through Polarity-Matched and -Mismatched
Daniel J Lee1, Majji Shankar1, Ayush Acharya1
1Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, United States.
Abstract:
Herein, we demonstrate that 2-alkenylarylaldimines and aryl-1,2-bisaldimines undergo polarity-matched and -mismatched 6π-azacarbo- (6π-AEC) and 6π-aza-azaelectrocyclization (6π-AAEC), respectively, by nitrogen to carbon (azacarbo) and nitrogen to nitrogen (aza-aza) bond formations to generate transient monoazabicyclo- and previously unknown 1,2-bisazabicyclo-o-quinodimethane (o-QDM) intermediates. The monoazabicyclo-o-quinodimethanes engage in a Diels-Alder/retro-Diels-Alder reaction to form substituted dimethyl naphthalene-2,3-dicarboxylates, while the 1,2-bisazabicyclo-o-quinodimethanes react in a Diels-Alder/N-N bond scission reaction to generate 1,4-bis(phenylamino)naphthalene-2,3-dicarboxylates. While polarity-matched 6π-AECs have been explored, polarity-mismatched 6π-AAECs have not been studied due to their complications with the nucleophilic character of iminyl nitrogens at the bond-forming termini.
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