The Wolff rearrangement uses either catalytic silver oxide, heat, or light to convert an α-diazo ketone to a ketene. In a one-step reaction, the catalyst initiates a 1,2-shift to release nitrogen gas and produce ketene. Due to the release of nitrogen gas, this reaction should not be performed in a closed system.

Lab Tips

  • Thermal catalysis is not ideal as delicate substrates may degrade and side reactions such as the direct displacement of the diazo group without rearrangement frequently occur. [1]
  • Photochemical activation is convenient and takes place even at low temperatures, but only if the product is not photolabile. [1]
  • Silver catalysts are generally used as they lower the required reaction temperature considerably compared to the thermal process. [1]
  • If the migrating group has a stereocenter, there is net retention of configuration after the migration. [1]
  • Cyclic diazo ketones undergo ring-contraction. [1]
  • Numerous side reactions are possible since α-diazo ketones are very reactive. Careful choice of reaction conditions can avoid/minimize these side reactions. [2,3]
1. Kürti, L., Czakó, B. (2005). Strategic Applications of Named Reactions in Organic Synthesis; Background and Detailed Mechanisms. Burlington, MA: Elsevier Academic Press.
2. Gill, G. B. The Wolff Rearrangement. Comp. Org. Synth. 1991, 3, 887-912.
3. Kirmse, W. 100 Years of the Wolff rearrangement. Eur. J. Org. Chem. 2002, 14, 2193-2256.


Top Citations

Original Paper

Related Reactions

  • Arndt-Eistert Synthesis

Related Compounds

By shuhan yang


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