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.