The Wolff rearrangement converts an α-diazocarbonyl compound into a ketene through loss of nitrogen and 1,2-migration. The ketene can then react with water, alcohols, amines, or carbon nucleophiles to deliver diverse products.
Initiation methods
Photochemical, thermal, and metal-catalyzed conditions are commonly used. The best choice depends on substrate sensitivity, desired selectivity, reaction scale, and the downstream ketene-trapping step.
Synthetic applications
The transformation underpins homologation strategies and ring-contraction chemistry. Careful control of irradiation, temperature, and trapping-agent concentration can minimize side reactions.