Wagner–Meerwein rearrangement

Source: Wikipedia, the free encyclopedia.

A Wagner–Meerwein rearrangement is a class of

aryl group migrates from one carbon to a neighboring carbon.[1]
Yegor Yegorovich Vagner; he had German origin and published in German journals as Georg Wagner; and Hans Meerwein
.

Several reviews have been published.[3][4][5][6][7]

The rearrangement was first discovered in

bicyclic terpenes for example the conversion of isoborneol to camphene:[8]

Dehydration of Isoborneol to Camphene
Dehydration of Isoborneol to Camphene

The story of the rearrangement reveals that many scientists were puzzled with this and related reactions and its close relationship to the discovery of

carbocations as intermediates.[9]

In a simple demonstration reaction of

3-methyl-2-butanol in sulfuric acid and acetic acid yields the same disubstituted product,[10]
the latter via a hydride shift of the cationic intermediate:

Carbocation rearrangement Polito 2010

Currently, there are works relating to the use of skeletal rearrangement in the synthesis of bridged azaheterocycles. These data are summarized in [11]

Some examples of Wagner-Meerwein rearrangement in heterocyclic series

Plausible mechanisms of the Wagner–Meerwein rearrangement of diepoxyisoindoles:

Plausible mechanisms of the Wagner-Meerwein rearrangement of diepoxyisoindoles

The related Nametkin rearrangement, named after

Sergey Namyotkin, involves the rearrangement of methyl groups in certain terpenes. In some cases the reaction type is also called a retropinacol rearrangement (see pinacol rearrangement
).

References

  1. Vagner, Ye. Ye. (Wagner, G.) (1899). "In "Protokol zasedaniya Otdeleniya Khimii R. F. Khimicheskago Obshchestva. 9-go sentyabrya 1899 goda [Minutes of the meeting of the Chemistry Section of the Russian Physical-Chemical Society. 9th September 1899]"". J. Russ. Phys. Chem. Soc. [Zh. Russ. Fiz.-Khim. O-va.] 31: 680–684.{{cite journal}}: CS1 maint: multiple names: authors list (link
    )
  2. doi:10.1002/jlac.19144050202
    .
  3. doi:10.1021/cr50020a004
    .
  4. doi:10.1021/ar50076a002
    .
  5. doi:10.1021/ar50098a001
    .
  6. ISBN 3-540-09309-5.{{cite journal}}: CS1 maint: multiple names: authors list (link
    )
  7. ISBN 978-0-08-052349-1
    .
  8. OCLC 642506595
  9. doi:10.1021/ed077p858
    .
  10. doi:10.1021/ed9000238
    .
  11. doi:10.1016/j.tet.2011.09.099
    .
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