Development of a Nickel-Catalyzed N–N Coupling for the Synthesis of Hydrazides

Abstract

A nickel-catalyzed N–N cross-coupling for the synthesis of hydrazides is reported. O-Benzoylated hydroxamates were efficiently coupled with a broad range of aryl and aliphatic amines via nickel catalysis to form hydrazides in an up to 81% yield. Experimental evidence implicates the intermediacy of electrophilic Ni-stabilized acyl nitrenoids and the formation of a Ni­(I) catalyst via silane-mediated reduction. This report constitutes the first example of an intermolecular N–N coupling compatible with secondary aliphatic amines.

Recent Advances in Catalytic Nitrogen–Nitrogen Bond Formation Reactions

“…Very recent, Reisman, Stoltz, and co-workers reported a nickel-catalyzed intermolecular N–N coupling reaction (Scheme ). This new nitrene-mediated N–N bond formation was achieved by the reaction between O -benzoylated hydroxamates 40 and aryl/aliphatic amines 41 in the presence of Ni half-sandwich catalysts, affording hydrazides 42 in up to 81% yield.…”

An iron-catalyzed nitrene transfer reaction of nitrosobenzenes with N-acyloxyamides for accessing N-acyl azoxy molecules

“…15 Employing O -benzoylated hydroxamates as acyl nitrene precursors, Stoltz and Reisman developed a nickel-catalyzed N–N coupling reaction which is compatible with aromatic and aliphatic amines. 16 Nitrosoarenes are highly reactivity organic precursors and could act as nucleophiles owing to the lone pair of electrons on the nitrogen atom. 17 However, to the best of our knowledge, the application of nitrosoarenes as nucleophiles in nitrene transfer reactions has not been reported so far.…”

Discovery of a Bacterial Hydrazine Transferase That Constructs the N-Aminolactam Pharmacophore in Albofungin Biosynthesis

“…These functional groups, including diazo, N-nitroso, triazole, hydrazine, hydrazone, hydrazide, and various others, are also found in hundreds of naturally occurring compounds that exhibit diverse biological activities and chemical structures (Figure a) . Due to the importance of these functional groups, both the synthetic and biological routes for creating N–N-containing functionality have garnered considerable attention. − …”