Pd(II)-Catalyzed Intramolecular Acetoxylative (3 + 2) Annulation of Propargylic Alcohol and Alkene: Polycyclic Oxa-heterocycle Synthesis and Mechanistic Insight.

A Pd(II)-catalyzed intramolecular and highly selective acetxoylative (3 + 2) annulation of propargylic alcohol and alkene is reported. Mechanistically, a hydroxy-guided regioselective alkyne acetoxypalladation is followed by 6-exo-trig alkene insertion to form an alkyl-Pd(II) intermediate. After oxidation, the resulting cyclometalated alkoxy-Pd(IV)-alkyl undergoes direct reductive elimination to afford a polycyclic oxa-heterocycle. When an additional coordinating site or ligand accessible by palladium is present, an SN2-type C-C reductive elimination of alkyl-Pd(IV) instead occurs along with hydroxy acetylation, affording 3-bicyclo[4.1.0]heptan-5-one products.