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Updated: May 27, 2025

Preparation of Stable Bicyclic Aziridinium Ions and Their Ring-Opening for the Synthesis of Azaheterocycles
Published on: August 22, 2018
Silver-mediated formal [4π + 2σ] cycloaddition reactions of bicyclobutanes with nitrile imines: access to
Huijuan Liao1, Jianyang Dong1, Xuechen Zhou1
1Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education and School of Chemistry and Chemical Engineering, Shaanxi Normal University Xi'an 710062 China jydong@snnu.edu.cn xuedong_welcome@snnu.edu.cn.
Abstract:
Despite recent advances in the synthesis of aza-bicyclo[3.1.1]heptanes (aza-BCHeps, which have an sp3-hybridized nitrogen atom) and azabicyclo[3.1.1]heptenes (aza-BCHepes, which have an sp2-hybridized nitrogen atom), which are bioisosteres of pyridine, construction of 2,3-diazobicyclo[3.1.1]heptenes (2,3-diazo-BCHepes), which have both sp2- and sp3-hybridized nitrogen atoms, has yet to be achieved. Herein, we disclose a method for silver-enabled formal [4π + 2σ] cycloaddition reactions between bicyclobutanes and nitrile imines (generated from hydrazonyl chlorides) to furnish a diverse array of 2,3-diazo-BCHepes, which feature both sp2- and sp3-hybridized nitrogen atoms embedded in a BCHepe framework. These compounds have the potential to serve as bioisosteres of both pyridines and pyridazines. Owing to the presence of the sp3-hybridized nitrogen, 2,3-diazo-BCHepes can be expected to exhibit geometries similar to those of aza-BCHepes and much better solubility. We demonstrated the synthetic utility of our method by carrying out a scaled-up reaction and diverse postcatalytic transformations.
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