Staudinger reaction



The Staudinger reaction or Staudinger reduction is a chemical reaction in which the combination of an triphenylphosphine oxide as the side product in addition to the amine.

The reaction was invented by and named after Hermann Staudinger.


An example of a Staudinger reduction is the organic synthesis of this pinwheel compound [3]:


Reaction mechanism

The phosphine at the terminal nitrogen atom of the azide and expulsion of nitrogen:

This intermediate is then hydrolyzed in the second step to the triphenylphosphine oxide.

Staudinger ligation

Developed by Saxon and Bertozzi in 2000, the Staudinger ligation is a modification of the classical Staudinger reaction in which an electrophilic trap (usually a methyl ester) is appropriately placed on the triaryl phosphine [4]. In the Staudinger ligation, the aza-ylide intermediate rearranges, in aqueous media, to produce an amide linkage and the phosphine oxide, and is so named the Staudinger ligation because it ligates the two molecules together, whereas in the classical Staudinger reaction, the two products are not covalently linked after hydrolysis.

The general schematic for the Staudinger ligation is shown below.

Applications

The Staudinger ligation has seen many applications in the field of chemical biology.

In one application this reaction is used to create a bond between a nucleoside and a fluorescent marker [5] [6] :

References

  1. ^ Staudinger, H.; Meyer, J. Helv. Chim. Acta 1919, 2, 635.
  2. ^ Gololobov, Y. G. et al. Tetrahedron 1981, 37, 437.
  3. ^ Preparation of 1,3,5-Tris(aminomethyl)-2,4,6-triethylbenzene from Two Versatile 1,3,5-Tri(halosubstituted) 2,4,6-Triethylbenzene Derivatives Karl J. Wallace, Robert Hanes, Eric Anslyn, Jeroni Morey, Kathleen V. Kilway, Jay Siegeld Synthesis 2005: 2080-2083. (Abstract)
  4. ^ Saxon, E.; Bertozzi, C.R. Science 2000, 287, 2007.
  5. ^ Synthesis of coumarin or ferrocene labeled nucleosides via Staudinger ligation Kosiova I, Janicova A, Kois P Beilstein Journal of Organic Chemistry, 2006 2:23 ( 30 November 2006 ) doi:10.1186/1860-5397-2-23
  6. ^ the nucleoside is based on deoxyuridine, the marker is a coumarin with a carboxyl group activated by HOBT
 
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