Photoinduced C−O Bond Formation through C−C Bond Cleavage of Alcohols by Suppressing Alcohol Oxidation

Abstract Herein, we present a photoinduced deconstructive alkoxyamination of alkyl alcohols catalyzed by iron salts. This transformation involves the initiation of alkoxy radicals through chlorine radical‐induced alkoxy radical formation, followed by β ‐scission and trapping of the resulting carbon radicals with 2,2,6,6‐tetramethylpiperidin‐1‐yl (TEMPO). This reaction exhibits a broad substrate scope (40 examples), including primary and secondary alcohols that are prone to oxidation by the combination of TEMPO and iron. Mechanistic investigations have revealed that enhanced coordination of the chloride ion with the iron center inhibits the OH oxidation process, thereby enabling the tolerance of primary and secondary alcohols.