Metal‐Catalysed Azidation of Organic Molecules

Abstract

The azide moiety is a desirable functionality in organic molecules, useful in a variety of transformations such as olefin aziridination, C–H bond amination, isocyanate synthesis, the Staudinger reaction and the formation of azo compounds. To harness the versatility of the azide functionality fully it is important that these compounds be easy to prepare, in a clean and cost‐effective manner. Conventional (non‐catalysed) methods to synthesise azides generally require quite harsh reaction conditions that are often not tolerant of functional groups. In the last decade, several metal‐catalysed azidations have been developed in attempts to circumvent this problem. These methods are generally faster, cleaner and more functional‐group‐tolerant than conventional methods to prepare azides, and can sometimes even be conveniently combined with one‐pot follow‐up transformations of the installed azide moiety. This review highlights metal‐catalysed approaches to azide synthesis, with a focus on the substrate scopes and mechanisms, as well as on advantages and disadvantages of the methods. Overall, metal‐catalysed azidation reactions provide shorter routes to a variety of potentially useful organic molecules containing the azide moiety.

Towards an Asymmetric Organocatalytic α-Azidation of β-Ketoesters

“…Organic azides are an important and versatile class of molecules, and their syntheses and applications have attracted considerable interest [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 ]. Their potential lies in the fact that these compounds can serve as valuable building blocks for further transformations, e.g., the direct syntheses of heterocycles by means of a 1,3-dipolar cycloaddition with alkynes [ 3 , 4 , 5 ], or their straightforward reduction to free amines [ 6 , 7 , 8 ] (to mention only a few thoroughly investigated prominent applications of azides).…”

“…Their potential lies in the fact that these compounds can serve as valuable building blocks for further transformations, e.g., the direct syntheses of heterocycles by means of a 1,3-dipolar cycloaddition with alkynes [ 3 , 4 , 5 ], or their straightforward reduction to free amines [ 6 , 7 , 8 ] (to mention only a few thoroughly investigated prominent applications of azides). Keeping this high potential in mind, it is no surprise that a variety of strategies to introduce azide functionalities in organic molecules have been reported [ 1 , 7 , 8 , 9 , 10 ]. The classical way of installing an azide group is based on the displacement of leaving groups, e.g., halides, by nucleophilic azide sources, like NaN 3 or trimethylsilylazide (TMSN 3 ) [ 11 ].…”

Transition Metal Catalyzed Azidation Reactions

“…Great improvements in the synthesis of organic azides have been achieved with the development of procedures based on the direct C-H functionalization [34][35][36]. Synthetic approaches based on the functionalization of ubiquitous and easily available C-H bonds have proven to be highly efficient for the preparation of many organic compounds.…”

Synthesis and characterization of azidated Adenopus breviflorus benth seed oil

“…Such compounds are good starting materials for preparing nitrogen heterocycles and they also serve as good synthons in click reactions (3). While many pure organic compounds have been azidated (4)(5)(6)(7)(8), there have been some reports on the synthesis of azido derivatives from pure fatty acids (3,(9)(10)(11). However, only a few studies on the azidation of complex unsaturated systems in plant oils (3,12,13) have been reported.…”