Hypervalent-iodine promoted selective cleavage of C(sp(3))-C(sp(3)) bonds in ethers

A visible-light-promoted and radical-mediated strategy for the site-specific cleavage of C(sp(3))-C(sp(3)) bonds in ethers is reported. Different cyclic and linear alkyl ethers are converted into benzoylated acetals and aldehydes or ketones under mild conditions in the presence of Ru(bpy)(3)Cl-2 as a photocatalyst and Zhdankin's lambda(3)-azidoiodane reagent in moderate to high yields. Control experiments and mechanistic investigations provide a plausible mechanism for this unusual deconstructive esterification of ethers.