Issue 20, 2021

Taming the reactivity of alkyl azides by intramolecular hydrogen bonding: site-selective conjugation of unhindered diazides

Abstract

Organic azides are still in the center of click chemistry connecting two molecules. However, taming the conjugation selectivity of azides is difficult without the help of bulky groups. We report herein the unique reactivities of α-azido secondary acetamides (α-AzSAs) as minimal and unhindered azide structures. The NH–azide interaction in the α-AzSAs, supposed by DFT calculations, allowed selective conjugation in the presence of other azido moieties, even without steric hindrance. With Staudinger–Bertozzi ligation, α-AzSAs underwent conjugation prior to the other primary alkyl azides. On the other hand, in propargyl cation-mediated triazole synthesis, other alkyl azides, including tertiary alkyl azides, underwent the conjugation faster than α-AzSAs. We also demonstrated site-selective integration of the functional components onto the diazide modular hubs.

Graphical abstract: Taming the reactivity of alkyl azides by intramolecular hydrogen bonding: site-selective conjugation of unhindered diazides

Supplementary files

Article information

Article type
Research Article
Submitted
25 Jūl. 2021
Accepted
11 Aug. 2021
First published
14 Aug. 2021

Org. Chem. Front., 2021,8, 5793-5803

Taming the reactivity of alkyl azides by intramolecular hydrogen bonding: site-selective conjugation of unhindered diazides

K. Maegawa, H. Tanimoto, S. Onishi, T. Tomohiro, T. Morimoto and K. Kakiuchi, Org. Chem. Front., 2021, 8, 5793 DOI: 10.1039/D1QO01088C

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