The Staudinger reaction uses a trivalent phosphorous compound such as triphenylphosphine, an organic azide, and water to make a primary amine. Triphenylphosphine first attacks the terminal nitrogen of the azide, creating a phosphazide intermediate, which undergoes a rearrangement to release nitrogen gas and form an iminophosphorane intermediate (also known as an aza-ylide or a phosphinimine). Hydrolysis with water gives rise to a 1° amine and a stable phosphine oxide.

  • Reagents: Trialkyl- or Triarylphosphine, Solvent (THF, Et2O), Water
  • Reactant: Alkyl-, Aryl-, or Heteroarylazide
  • Product: 1° Amine
  • Type of Reaction: Nucleophilic Addition and Rearrangement
  • Bond Formation: NH

Lab Tips

  • Quantitative yields are obtained without the formation of side products.
  • Trivalent phosphorous compounds with O-alkyl, O-aryl, NH2, NR2, Cl, F, NCO, or any combination of these ligands also undergo the reaction.
  • Iminophosphorane intermediates derived from alkyl- or aryl- azides and phosphines ae stable enough to be isolated, but alkoxy groups on the phosphorus atom tend to undergo alkyl migration.
  • Iminophosphoranes are versatile synthetic intermediates, reacting with: (i) carbonyl or thiocarbonyl compounds to yield imines (aza-Wittig reaction), (ii) carboxylic acids to afford N-substituted amides, (iii) acyl halides to generate imidoyl halides, etc.
Kürti, L., Czakó, B. (2005). Strategic Applications of Named Reactions in Organic Synthesis; Background and Detailed Mechanisms. Burlington, MA: Elsevier Academic.


Top Citations

Original Paper

Related Reactions

  • Appel Reaction
  • Delepine Reaction
  • Eschweiler-Clarke Reaction
  • Gabriel Synthesis
  • Mitsunobu Reaction

Related Compounds

  • PR3 Compound
By shuhan yang


Just added to your wishlist:
My Wishlist
You've just added this product to the cart:
Go to cart page