Issue 15, 2025

Nitrene-mediated aminative N–N–N coupling: facile access to triazene 1-oxides

Abstract

Significant progress has been made in metal-catalyzed cross-coupling reactions over the past few decades. However, the development of innovative aminative coupling strategies remains highly desirable. Herein, we report a nitrene-mediated aminative N–N–N coupling reaction that leverages an anomeric amide as a key reagent to bridge amines with nitrosoarenes. This strategy enables the in situ generation of an aminonitrene intermediate, which is efficiently intercepted by nitrosoarenes, providing a direct, mild, and highly efficient route to triazene 1-oxides. Mechanistic investigations reveal that the N-substituents of the amine play a crucial role in modulating the reactivity of the aminonitrene intermediate. Complementary computational studies further indicate that aminonitrene acts as a nucleophile, while nitrosobenzene serves as an electrophile. Notably, aminonitrene–nitrosoarene coupling is significantly favored due to a substantial reduction in distortion energy, effectively outcompeting the nitrene dimerization pathway.

Graphical abstract: Nitrene-mediated aminative N–N–N coupling: facile access to triazene 1-oxides

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Article information

Article type
Edge Article
Submitted
07 Jan 2025
Accepted
09 Mar 2025
First published
10 Mar 2025
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2025,16, 6458-6467

Nitrene-mediated aminative N–N–N coupling: facile access to triazene 1-oxides

S. Zhu, H. Zhang, B. Sun, Z. Bai, G. He, G. Chen and H. Wang, Chem. Sci., 2025, 16, 6458 DOI: 10.1039/D5SC00064E

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