Catalyst-Free Rearrangement of Allenyl Aryldiazoacetates into 1,5-Dihydro‑4H‑pyrazol-4-ones

Phenylpropargyl diazoacetates exist in equilibrium with 1-phenyl-1,2-dien-1-yl diazoacetate - allenes that are rapidly formed at room temperature through 1,3-acyloxy migration catalyzed by gold­(I) or gold­(III) compounds, and these catalysts react solely with the π-donor rather than with the diazo group. The product allene of the aryl­diazo­acetates undergoes rearrangement that is not catalyzed by gold in which the terminal nitrogen of the diazo functional group adds to the central carbon of the allene, initiating a sequence of bond-forming reactions, resulting in the production of 1,5-dihydro-4H-pyrazol-4-ones in good yields. These 1,5-dihydro-4H-pyrazol-4-ones undergo intramolecular 1,3-acyl migration to form an equilibrium mixture and can quantitatively transfer the acyl group to an external nucleophile with formation of 4-hydroxy­pyrazoles. Reactions of phenyl­propargyl phenyl­diazo­acetates catalyzed by cationic gold complexes are initiated at the diazo functional group to form a gold carbene whose subsequent cascade process (intramolecular addition, then aromatic substitution) results in the formation of a product that is uniquely characteristic of this pathway.