Organic azides: “energetic reagents” for the intermolecular amination of C–H bonds

Abstract

This feature article provides an overview of the application of organic azides for the intermolecular amination of sp(3) and sp(2) C-H bonds. The catalytic activity of several metal complexes was reviewed underlining both synthetic and mechanistic aspects of the C-H amination. The majority of the aminated compounds reported in literature have been collected in this paper to provide a compendium of published procedures. In addition, the discussion of involved mechanisms has been included to assist the reader to envisage the future potential of organic azides in the synthesis of aza-derivatives.

A mechanistic investigation of the ruthenium porphyrin catalysed aziridination of olefins by aryl azides

“…18,19 In the last few decades a large number of examples of this reaction were reported using iminoiodinanes (PhI = NR) as nitrene sources in the presence of a variety of metal catalysts, e.g., porphyrin, bis-oxazoline and Schiff base complexes. [21][22][23][24][25][26][27][28] Many reports were published concerning the aziridination of olefins by organic azides 26,[29][30][31][32][33][34][35] and excellent results in terms of yields and enantioselectivities were achieved by Katsuki's [36][37][38] and Zhang's 39,40 groups. 11,12 More recently, organic azides (RN 3 ) have been extensively used as nitrene precursors thanks to their atom efficiency related to the formation of N 2 as the only by-product of the nitrene transfer reaction.…”

Reactive Extrusion Strategies to Fabricate Magnetite–Polyethylene Nanocomposites with Enhanced Mechanical and Magnetic Hyperthermia Properties

“…As previously reported, azidosilane coupling agents can bind to thermoplastic polymers through a nitrene‐mediated CH bond amination process, which can be facilitated by thermal activation and/or transition metal catalysis . In this case, the high level of Fe ions available from the MNPs can serve as the catalyst during the azide coupling reaction between the MNP@Az fillers and the PE backbone.…”

Application of [Co(Corrole)]– Complexes in Ring‐Closing C–H Amination of Aliphatic Azides via Nitrene Radical Intermediates

“…In this method a metal catalyst activates a nitrene precursor to form a metallo‐nitrene intermediate. Depending on its reactivity, this metallo‐nitrene intermediate can insert into challenging bonds, such as thermodynamically and kinetically stable C–H bonds . Organic azides are particularly attractive nitrene precursors in this regard, as they are easy to synthesise and generate only N 2 as a waste product in the amination step , .…”