Photoinduced Ligand-to-Metal Charge Transfer (LMCT) of Fe Alkoxide Enabled C–C Bond Cleavage and Amination of Unstrained Cyclic Alcohols

We report an alkoxy radical process for the C–C bond cleavage and functionalization of unstrained tertiary and secondary cyclic alcohols. In the absence of a chlorine atom, the readily available iron catalysts [Fe­(OBu-t)₃ or Fe­(acac)₃/t-BuONa] facilitate alkoxy radical formation via the direct ligand-to-metal charge transfer of Fe alkoxide and further enable the ring opening and amination of cyclic alcohols. The remote amino carbonyl compounds could be obtained with a broad scope in up to excellent yields under the mildly redox-neutral system. Light-driven electron transfer, alkoxy radical formation, and subsequent C–C bond cleavage via β-scission were the keys to the transformation.