Palladium-Catalyzed Formal (5 + 6) Cycloaddition of Vinylethylene Carbonates with Isatoic Anhydrides for the Synthesis of Medium-Sized N,O-Containing Heterocycles.

Under the reaction conditions of Pd(PPh3)4 (2.5 mol %) and PPh3 (10 mol %) in EtOAc at 60 °C, the formal (5 + 6) cycloaddition of vinylethylene carbonates with isatoic anhydrides proceeded smoothly and furnished medium-sized N,O-containing heterocycles in reasonable chemical yields. The chemical structures of the title products were clearly identified by X-ray diffraction analysis.

Asymmetric Synthesis of Spiropyrazolones via Chiral Pd(0)/Ligand Complex-Catalyzed Formal [4+2] Cycloaddition of Vinyl Benzoxazinanones with Alkylidene Pyrazolones.

In the presence of the chiral Pd(0)/ligand complex, vinyl benzoxazinanones underwent the [4+2] cycloaddition with alkylidene pyrazolones smoothly and delivered spiropyrazolones in reasonable yields, diastereoselectivities, and eneantioselectivities (up to >99% yield, >99:1 dr and 99% ee). The absolute configuration of the obtained spiropyrazolones was unambiguously characterized with the use of X-ray single-crystal structure analysis. Moreover, the reaction mechanism was assumed to interpret the formation of the target compounds.