Hypervalent-iodine promoted selective cleavage of C(sp3)–C(sp3) bonds in ethers

Abstract

A visible-light-promoted and radical-mediated strategy for the site-specific cleavage of C(sp³)–C(sp³) 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)₃Cl₂ as a photocatalyst and Zhdankin's λ³-azidoiodane reagent in moderate to high yields. Control experiments and mechanistic investigations provide a plausible mechanism for this unusual deconstructive esterification of ethers.