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.