Sequential C-F Bond Transformation of the Difluoromethylene Unit in Perfluoroalkyl Groups: A Combination of Fine-Tuned Phenothiazine Photoredox Catalyst and Lewis Acid.

ABSTRACT

A sequential process via photoredox catalysis and Lewis acid mediation for C-F bond transformation of the CF2 unit in perfluoroalkyl groups has been achieved to transform perfluoroalkylarenes into complex fluoroalkylated compounds. A phenothiazine-based photocatalyst promotes the defluoroaminoxylation of perfluoroalkylarenes with (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) under visible light irradiation, affording the corresponding aminoxylated products. These products undergo a further defluorinative transformation with various organosilicon reagents mediated by AlCl3 to provide highly functionalized perfluoroalkyl alcohols. Our novel phenothiazine catalyst works efficiently in the defluoroaminoxylation. Transient absorption spectroscopy revealed that the catalyst regeneration step is crucial for the photocatalytic aminoxylation.