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 júl. 2021
Accepted
11 ágú. 2021
First published
14 ágú. 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

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements