Base-Promoted Homolytic Aromatic Substitution (BHAS) Reactions and Hydrodehalogenations Driven by Green Light and an Iron(III)-NHC Photoredox Catalyst.

Abstract

An Fe(III)-NHC complex has been employed for the green light driven catalysis of base-promoted homolytic aromatic substitution (BHAS) reactions. Tributylamine was used as a sacrificial electron donor, together with a potassium carbonate base in dimethyl sulfoxide as solvent. In contrast to previously studied photocatalysts, the excited Fe(III)-NHC complex is not reducing the arylhalide substrates. Instead, the latter are activated by α-aminoalkyl radicals formed upon reductive quenching of the photocatalyst by tributylamine. Avoiding strongly reducing photocatalysts as well as strong base, these mild reaction conditions allowed for the expansion of the substrate scope to accommodate also aldehyde and ester substituents. 100% conversion was obtained after 48 hrs of irradiation. In this way a wide variety of cyclized products and their corresponding hydrodehalogenated products were obtained as isolated and pure compounds, in the vast majority of cases.