Schmidt Reaction

The acid-catalysed reaction of hydrogen azide with electrophiles, such as carbonyl compounds, tertiary alcohols or alkenes. After a rearrangement and extrusion of N₂, amines, nitriles, amides or imines are produced.

---

Mechanism of the Schmidt Reaction

Reaction of carboxylic acids gives acyl azides, which rearrange to isocyanates, and these may be hydrolyzed to carbamic acid or solvolysed to carbamates. Decarboxylation leads to amines.

The reaction with a ketone gives an azidohydrin intermediate, which rearranges to form an amide:

Alkenes are able to undergo addition of HN₃ as with any HX reagent, and the resulting alkyl azide can rearrange to form an imine:

Tertiary alcohols give substitution by azide via a carbenium ion, and the resulting alkyl azide can rearrange to form an imine.

Recent Literature

Chemoselective Schmidt Reaction Mediated by Triflic Acid: Selective Synthesis of Nitriles from Aldehydes

Tf₂O-Promoted Intramolecular Schmidt Reaction of the ω-Azido Carboxylic Acids

Efficient, One-Pot, BF₃·OEt₂-Mediated Synthesis of Substituted N-Aryl Lactams

Interruption of Formal Schmidt Rearrangement/Hosomi-Sakurai Reaction of Vinyl Azides with Allyl/Propargylsilanes

Gold(I)-Catalyzed Intramolecular Acetylenic Schmidt Reaction