Transition Metal Catalyzed Azidation Reactions

Abstract

A wide range of methodologies for the preparation of organic azides has been reported in the literature for many decades, due to their interest as building blocks for different transformations and their applications in biology as well as in materials science. More recently, with the spread of the use of transition metal-catalyzed reactions, new perspectives have also materialized in azidation processes, especially concerning the azidation of C–H bonds and direct difunctionalization of multiple carbon-carbon bonds. In this review, special emphasis will be placed on reactions involving substrates bearing a leaving group, hydroazidation reactions and azidation reactions that proceed with the formation of more than one bond. Further reactions for the preparation of allyl and vinyl azides as well as for azidations involving the opening of a ring complete the classification of the material.

Regioselective C–H Azidation of Anilines and Application to Synthesis of Key Intermediate for Pharmaceutical

“…Regarding C–H azidation of anilines, a limited number of literature precedents were available in comparison with aliphatic couterparts (Scheme ). Jiao et al reported a pioneering work on copper-catalyzed C–H azidation employing CuBr and TBHP .…”

New Strategies for the Synthesis of Aliphatic Azides

“…Mechanistic studies suggest that this reaction involves Mn-catalyzed alkyl radical formation and subsequent azidyl group transfer through Mn III/IV electrocatalysis, which avoids the oxidation to carbocation thus minimizing the side reactions leading to oxygenated products. In addition to these new research articles, we also found a few new review articles that were published during the manuscript review process. − …”

C–H functionalization of aromatic amines for azidation catalyzed by Betti base coordinated copper(ii) complexes under ultrasonication

“…5 However, owing to their inert aromatic C–H bonds the synthesis of aromatic azides is limited in the literature, unlike aliphatic azides. 6–9…”

“…5 However, owing to their inert aromatic C-H bonds the synthesis of aromatic azides is limited in the literature, unlike aliphatic azides. [6][7][8][9] Interestingly, it was found that copper can facilitate the synthesis of aromatic azides via C-H functionalization. Aniline, a simple aromatic amine, was converted into its corresponding mono-and di-azides using CuBr (10 mol%) with a yield of 46% and 27%, respectively.…”