Lobry de Bruyn-van Ekenstein Rearrangement

The Lobry de Bruyn–van Ekenstein rearrangement is a classic carbohydrate reaction where aldoses and ketoses interconvert via an enediol intermediate, often under alkaline conditions. It explains the equilibrium between glucose, fructose, and mannose, and has important applications in sugar chemistry, food chemistry, and biochemistry.

The reaction is named after Cornelis Adriaan Lobry van Troostenburg de Bruyn and Willem Alberda van Ekenstein who reported it in 1895.

Diagram of Lobry de Bruyn–van Ekenstein rearrangement showing glucose interconversion to fructose and mannose via enediol intermediate

Mechanism

  • Deprotonation: Hydroxide ion abstracts a proton from the α-carbon of the sugar.
  • Enediol Formation: This generates an enediol intermediate (–C(OH)=C(OH)–).
  • Reprotonation: The enediol can be reprotonated at different positions, leading to:
    • Isomerization: Aldose ↔ Ketose (e.g., glucose ↔ fructose).
    • Epimerization: Formation of stereoisomers (e.g., glucose ↔ mannose).
Steo by step Mechanism of the Lobry-de Bruyn-van Ekenstein Rearrangement

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