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 keys to the transformation. subsequent C-C bond cleavage via beta-scission were the keys to the transformation.

Automated summary

This study reports an alkoxy radical process for the C-C bond cleavage and functionalization of unstrained tertiary and secondary cyclic alcohols. Iron catalysts facilitate alkoxy radical formation and enable the ring opening and amination of cyclic alcohols. The method allows for the synthesis of remote amino carbonyl compounds in a wide scope and with excellent yields under mild conditions.