Methylene Insertion into Nitrogen-Heteroatom Single Bonds of 1,2-Azoles via a Zinc Carbenoid: An Alternative Tool for Skeletal Editing

The nitrogen-heteroatom single bonds of 1,2-azoles and isoxazolines underwent methylene insertion in the presence of CH(2) I(2) (6 equiv.) and diethylzinc (3 equiv.) to produce a wide variety of the ring-expanded six-membered heterocycles. Density functional theory calculations suggest that the methylene insertion proceeds via cleavage of nitrogen-heteroatom single bonds followed by ring closure.