Fluoro Aryl Azides: Synthesis, Reactions and Applications

Abstract

Background: The complex photochemistry of aryl azides has fascinated scientists for several decades. Spectroscopists have investigated the intermediates formed by different analytical techniques. Theoretical chemists have explained the intrinsic interplay of intermediates under different experimental conditions. Objective & Method: A more complete understanding about the photochemistry of a given fluoro aryl azide is a basic requisite for its use in chemistry. In this review, we will discuss the synthesis of several fluoro substituted aryl azides and the reactions and intermediates generated upon photolysis and thermolysis of these azides and some examples of their applications in photoaffinity labeling and organic synthesis. Conclusion: In spite of the extensive research on the photochemistry of fluoro aryl azides, there are some areas that remain to be investigated. The application of this reaction in the synthesis of novel heterocyclic compounds has not been fully studied. Since fluorophenyl azides are known to undergo C-H and N-H insertion reactions, they could be used to prepare new fluorinated molecules or in the biochemical process known as photoaffinity labeling.

Synthesis of nitrophenyl and fluorophenyl azides and diazides by SNAr under phase‐transfer or microwave irradiation: Fast and mild methodologies to prepare photoaffinity labeling, crosslinking, and click chemistry reagents

“…In polymer modifications and material science diazide compounds are particularly important for crosslinking experiments. [ 3 ]…”

“…All the azides reported in this article have been prepared by other methodologies, and they were characterized by UV‐VIS, IR, NMR spectroscopy, and mass spectrometry to confirm their structure. [ 2,3,8–13,16,31,32 ] All aryl azides give two strong bands in IR (around 2100 cm −1 ) due to symmetric and asymmetric stretching of azide group (N 3 ). The purity of aryl azides was verified by melting point and/or 1 H NMR spectroscopy.…”

“…Theoretical chemists have studied the intrinsic interplay of intermediates formed under different reaction conditions. [ 3 ] Nitro‐ and fluoro‐substituted aromatic azides have found applications in several areas of chemistry such as synthesis of heterocyclic compounds, [ 4 ] polymer chemistry as crosslinking agents, [ 5 ] and biochemistry as photoaffinity labeling reagents. [ 6 ] Due to their physicochemical properties, fluorophenyl azides have been applied in different areas of organic and material science.…”

Photoaffinity Labeling Chemistries Used to Map Biomolecular Interactions

“…There are relatively few examples of their use in PAL experiments, but they were recently adapted for use in proximity labeling (Figure 3E). [72,73,124,125] 8. Tetrazoles 2,5-Disubstituted tetrazoles are an emerging PAL chemistry developed in recent years.…”

Photoacid Generators Activated through Sequential Two-Photon Excitation: 1-Sulfonatoxy-2-alkoxyanthraquinone Derivatives

“…Photochemical generation of reactive intermediates such as radicals, − nitrenes, − cations, − bases, , and protons − is a method for initiating useful chemical reactions that require high spatiotemporal specificity. The specificity from photochemical processes enables applications in numerous areas including photopharmacology, photoimaging, and photolithography.…”