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Updated: Aug 30, 2026

Preparation of Stable Bicyclic Aziridinium Ions and Their Ring-Opening for the Synthesis of Azaheterocycles
Published on: August 22, 2018
Density functional theory study of the intramolecular [2 + 3] cycloaddition of azide to nitriles
Fahmi Himo1, Zachary P Demko, Louis Noodleman
1Department of Molecular Biology, TPC-15, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037, USA.
Abstract:
Density functional theory calculations using the hybrid functional B3LYP have been performed to study tetrazole formation by intramolecular [2 + 3] dipolar cycloaddition of organic azides and nitriles. Experimental reactivity trends are explained and rationalized in terms of a number of parameters, such as strain, tether length, and solvation and entropy effects. Interestingly, no correlation was found between the overall free energies and the free energies of activation of the reactions, due to the significant difference in strain and geometry between the transition states and products.
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