Activation of N−O σ Bonds with Transition Metals: A Versatile Platform for Organic Synthesis and C−N Bonds Formation**

Abstract

N−O σ bonds containing compounds are versatile substrates for organic synthesis under transition metal catalysis. Their ability to react through both polar (oxidative addition, formation of metallanitrene, nucleophilic substitution) and radical pathways (single electron transfer, homolytic bond scission) have triggered the development of various synthetic methodologies, particularly toward synthesizing nitrogen‐containing compounds. In this review, we discuss the different modes of activation of N−O bonds in the presence of transition metal catalysts, emphasizing the experimental and computational mechanistic proofs in the literature to help to design new synthetic pathways toward the synthesis of C−N bonds.

Copper-catalyzed crosscoupling of vinyl nitrenes and CF3-carbenes to synthesize CF3-2-azadienes

“…9 Furthermore, employing α-CF 3 - N -tosylhydrazones as carbene precursors offers the possibility of not only coupling them with nitrenes but also introducing CF 3 groups into molecules, which are difficult to achieve using other available methods. 10 Conversely, several representative nitrene precursors, such as azides, 11 arylsulfonyl hydroxylamines, 12 amines, 13 and nitro compounds, 14 take part in amination reactions through denitrogenation, α -elimination, oxidation, and deoxygenation reduction processes. For instance, the Chiba and Jiao groups employed vinyl azides as vinyl nitrene precursors to synthesize aza-heterocycles and N -containing molecules.…”