Transition-Metal-Free Photoredox Phosphonation of Aryl C–N and C–X Bonds in Aqueous Solvent Mixtures

Abstract

Herein, we present an efficient and mild methodology for the synthesis of aromatic phosphonate esters in good to excellent yields using 10<i>H</i>-phenothiazine, an inexpensive commodity chemical, as a photoredox catalyst. The reaction exhibits wide functional group compatibility enabling the transformation in the presence of ketone, amide, ester, amine, and alcohol moieties. Importantly, the reaction proceeds using a green solvent mixture primarily composed of water, thus lowering the environmental footprint of this transformation compared to current methods. The transformation also proceeds under atmospheric conditions, which further differentiates it from current methods that require inert atmosphere. Mechanistic work using fluorescence quenching experiments and radical trapping approaches support the proposed mechanism.