Molecular Rearrangements
Principles
W: migrating group
A: migration origin
B: migration terminus
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Principles
• Types of migration
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Principles
• Types of rearrangements
Intramolecular
Intermolecular
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Rearrangement to Electron-Deficient Carbon
a) Carbon migration
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Rearrangement to Electron-Deficient Carbon
a) Carbon migration
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Rearrangement to Electron-Deficient Carbon
a) Carbon migration
The carbocation may be generated in a variety of ways:
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Rearrangement to Electron-Deficient Carbon
a) Carbon migration
The carbocation may be generated in a variety of ways:
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Rearrangement to Electron-Deficient Carbon
Hydrogen can also migrate
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Rearrangement to Electron-Deficient Carbon
Aryl groups have a far greater migratory aptitude than alkyl
groups or hydrogen
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Rearrangement to Electron-Deficient Carbon
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Rearrangement to Electron-Deficient Carbon
The rearrangement is stereospecific
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Rearrangement to Electron-Deficient Carbon
Two or more rearrangements may occur successively
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Rearrangement to Electron-Deficient Carbon
a) Carbon migration
Importance of the choice
of acid catalyst
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Rearrangement to Electron-Deficient Carbon
a) Carbon migration
ii) Pinacol rearrangement
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Rearrangement to Electron-Deficient Carbon
a) Carbon migration
ii) Pinacol rearrangement
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Rearrangement to Electron-Deficient Carbon
a) Carbon migration
ii) Pinacol rearrangement; the reaction occurs in an anti manner
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Rearrangement to Electron-Deficient Carbon
a) Carbon migration
ii) Pinacol rearrangement
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Rearrangement to Electron-Deficient Carbon
a) Carbon migration
iii) Benzilic acid rearrangement
benzil
benzilic acid
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Rearrangement to Electron-Deficient Carbon
a) Carbon migration
iv) Rearrangements involving diazomethane
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Rearrangement to Electron-Deficient Carbon
a) Carbon migration
iv) Rearrangements involving diazomethane
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Rearrangement to Electron-Deficient Carbon
a) Carbon migration
iv) Rearrangements involving diazomethane
Arndt-Eistert homologation
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Rearrangement to Electron-Deficient Carbon
a) Carbon migration
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Rearrangement to Electron-Deficient Carbon
a) Carbon migration
v) Rearrangements of alkanes
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Rearrangement to Electron-Deficient Carbon
a) Halogen, oxygen, sulfur and nitrogen migration
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Rearrangement to Electron-Deficient Carbon
a) Halogen, oxygen, sulfur and nitrogen migration
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Rearrangement to Electron-Deficient Nitrogen
a) The Hofmann, Curtius, Schmidt and Lossen rearrangements
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Rearrangement to Electron-Deficient Nitrogen
i) Hofmann rearrangement
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Rearrangement to Electron-Deficient Nitrogen
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Rearrangement to Electron-Deficient Nitrogen
ii) Curtius rearrangement
Acid azides decompose on being heated to give isocyanates:
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Rearrangement to Electron-Deficient Nitrogen
ii) Curtius rearrangement
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Rearrangement to Electron-Deficient Nitrogen
iii) Schmidt rearrangement
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Rearrangement to Electron-Deficient Nitrogen
iv) Lossen rearrangement
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Rearrangement to Electron-Deficient Nitrogen
a) The Hofmann, Curtius, Schmidt and Lossen rearrangements
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Rearrangement to Electron-Deficient Nitrogen
b) The Beckmann rearrangement
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Rearrangement to Electron-Deficient Nitrogen
b) The Beckmann rearrangement
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Rearrangement to Electron-Deficient Nitrogen
b) The Beckmann rearrangement
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Rearrangement to Electron-Deficient Oxygen
a) Baeyer-Villiger reaction
Conversion of ketones to esters and cyclic ketones to lactones
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Rearrangement to Electron-Deficient Oxygen
a) Baeyer-Villiger reaction
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Rearrangement to Electron-Deficient Oxygen
b) Acid-catalyzed rearrangement of tertiary hydroperoxides
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Rearrangement to Electron-Deficient Oxygen
c) Dakin reaction
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Rearrangement to Electron-Rich Carbon
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Rearrangement to Electron-Rich Carbon
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Rearrangement to Electron-Rich Carbon
i) Stevens rearrangement
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Rearrangement to Electron-Rich Carbon
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Rearrangement to Electron-Rich Carbon
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Rearrangement to Electron-Rich Carbon
iii) Favorskii rearrangement
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Rearrangement to Electron-Rich Carbon
iii) Favorskii rearrangement
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Aromatic Rearrangements
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Aromatic Rearrangements
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Aromatic Rearrangements
a) Intermolecular migration from nitrogen to carbon
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Aromatic Rearrangements
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Aromatic Rearrangements
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Aromatic Rearrangements
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