Annulation of Alkynyl Aryl Ethers with Allyl Pivalates To Give 2,3-Bismethylenechromanes through Double C-H Bond Cleavage.

The treatment of silylethynyloxyarenes with allylic pivalates in the presence of a palladium catalyst led to efficient C-H bond cleavage in both substrates and a novel annulation reaction to give 2,3-bismethylenechromanes. When ortho-allylated silylethynyloxybenzenes were used as the substrates, the same products were obtained. This result shows that site-selective intramolecular hydrovinylation is involved in the annulation reaction. The synthetic utility of the products was demonstrated by the construction of condensed polycycles.