Parallel Synthesis of Pyrazolone-Fused Cinnolines by the Palladium-Catalyzed [4+2] Annulation of Pyrazol-3-ones with Substituted Allenoates

The synthesis of pyrazolone-fused cinnolines from pyrazol-3-ones and alpha,gamma-substituted allenoates via a palladium-catalyzed C-H activation/annulation cascade was developed. Mechanistic studies revealed the course of the reaction. Initially, N-acyl-valine ligand-assisted ortho-C-H activation gives ortho-alkenylated intermediate. Subsequent cyclopalladation and migratory insertion of allenoate give a seven-membered palladacycle. Reductive elimination finally furnishes pyrazolone-fused cinnolines.