Oxygen Migration into Carbon–Carbon Single Bonds by Photochemical Oxidation

The editing of organic molecules through single-atom modifications is an enabling capability for medicinal chemistry. While several examples of single-atom insertions into the carbon–carbon double bonds of unsaturated aromatic ring systems have been reported, heteroatom insertions into chemically inert carbon–carbon single bonds are comparatively rare. We report herein a photochemical strategy for formal migration of oxygen atoms into carbon–carbon single bonds. This protocol is based on the ability of copper(II) salts to induce photochemical homolytic cleavage of carbon–carbon bonds adjacent to alcohols and to mediate oxidative coupling reactions of the resulting organoradical intermediates. Application of this method to cyclic alcohol substrates results in oxygen-atom insertions into saturated carbocyclic rings, and its extension to linear alcohol substrates enables atomic permutation of hydroxymethyl functionalities into methyl ethers.