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Neighboring Nitrogen Atom-Induced Reactions of Azidoacetyl Hydrazides, including Unexpected Nitrogen-Nitrogen Bond Cleavage of the Hydrazide

Hiroki Tanimoto, Ryo Adachi, Aoi Otsuki, Takenori Tomohiro

Organics · pp. 520–533 · Published 19 Dec 2022

10.3390/org3040035

Abstract

We studied the hydrazide compounds of the α-azidoacetyl group, which showed specific click reactivity by the intramolecular hydrogen bonding between the azido group and the N-H of the hydrazide moiety. In the competitive click reactions with a general alkyl azide, both traceless and non-traceless Staudinger-Bertozzi ligation occurred azide-site-selectively by the acceleration effect of the hydrogen bonding. However, the product obtained from the traceless reaction was further transformed into heterocyclic compounds. In addition, in an attempt at a synthesis of naphthalimide-possessing azidoacetyl hydrazide, nitrogen-nitrogen bond cleavage of the azidoacetyl hydrazides occurred to give the reduced amine product. These unexpected results could help design molecules for the successful Staudinger-Bertozzi ligation of the hydrazide compounds and develop a new nitrogen-nitrogen bond cleavage method.

Hydrazide Chemistry Azide Alkyl Moiety Nitrogen Reactivity (psychology) Hydrogen bond

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Cited by 4

Site-Selective Staudinger Conjugation of Aryl Azides Driven by Intramolecular Hydrogen Bonding

Hiroki Tanimoto, Teruki Ishihara, Asuka Yotsu · Chemical and Pharmaceutical Bulletin · 2025

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