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:McFadyen–Stevens reaction

{{Short description|Chemical reaction}}

The McFadyen–Stevens reaction is a chemical reaction best described as a base-catalyzed thermal decomposition of acylsulfonylhydrazides to aldehydes.{{Ref|McFadyen1936}}{{Ref|Mosettig1954}}

Image:McFadyen-Stevens Reaction Scheme.png

Dudman et al. have developed an alternative hydrazide reagent.{{Ref|Dudman1980}}

Reaction mechanism

The mechanism of the McFadyen–Stevens reaction is still under investigation. Two groups have independently proposed a heterolytic fragmentation mechanism.{{Ref|Brown1958}}{{Ref|Campaigne1959}} The mechanism involves the deprotonation of the acyl sulfonamide followed by a 1,2-hydride migration to give the alkoxide (3). The collapse of the alkoxide results in the fragmentation producing the desired aldehyde (4), nitrogen gas, and an aryl sulfinate ion (5).

Image:McFadyen-Stevens Reaction Mechanism.png

Martin et al. have proposed a different mechanism involving an acyl nitrene.{{Ref|Martin1974}}

See also

References

  1. {{Note|McFadyen1936}} {{cite journal|author1=McFadyen, J. S. |author2=Stevens, T. S. |journal=J. Chem. Soc.|year=1936|pages= 584|doi= 10.1039/jr9360000584|title= 128. A new method for the conversion of acids into aldehydes}}
  2. {{Note|Mosettig1954}} {{cite book|author= Mosettig, E. |title=Org. React.|year=1954|volume=8|pages= 232–240|doi=10.1002/0471264180.or008.05|chapter=The Synthesis of Aldehydes from Carboxylic Acids|isbn=0471264180}}
  3. {{Note|Dudman1980}} {{cite journal|author= Dudman, C. C.|journal=Tetrahedron Lett.|year=1980|pages= 4645|doi= 10.1016/0040-4039(80)80096-7|title= Use of 2,4,6-tri-isopropylbenzenesulphonyl hydrazide in the mcfadyen-stevens aldehyde synthesis|first2= Peter |last2=Grice|first3= Colin B. |last3=Reese|volume= 21|issue= 48|display-authors=etal }}
  4. {{Note|Brown1958}} {{cite journal|author1=Brown, V. M. |author2=Carter, P. H. |author3=Tomlinson, M. |journal=J. Chem. Soc.|year=1958|pages= 1843|doi= 10.1039/jr9580001843|title= 374. Formyl compounds. Part II}}
  5. {{Note|Campaigne1959}} {{cite journal|author1=Campaigne, E. |author2=Thompson, R. L. |author3=Van Werth, J. E. |journal=J. Med. Chem.|year=1959|volume=1|pages= 577–599|doi= 10.1021/jm50007a003|title= Some Heterocyclic Aldehyde Thiosemicarbazones Possing Anti-viral Activity|issue= 6|pmid=13807198 }}
  6. {{Note|Martin1974}} {{cite journal|author1=Martin, S. B. |author2=Craig, J. C. |author3=Chan, R. P. K. |doi=10.1021/jo00929a600|title= An Investigation of the McFadyen-Stevens Reaction|year= 1974|journal= The Journal of Organic Chemistry|volume= 39|issue= 15|pages= 2285}}

{{DEFAULTSORT:McFadyen-Stevens reaction}}

Category:Organic redox reactions

Category:Rearrangement reactions

Category:Name reactions