A One‐Pot Approach for Bio‐Based Arylamines via a Combined Photooxidative Dearomatization‐Rearomatization Strategy

The synthesis of arylamines from renewable resources under mild reaction conditions is highly desired for the sustainability of the chemical industry, where the production of hazardous waste is a prime concern. However, to date, there are very few tools in chemists’ toolboxes that are able to produce arylamines in a sustainable manner. Herein, a robust one‐pot approach for constructing bio‐based arylamines via a combined photooxidative dearomatization‐rearomatization strategy is presented. The developed methodology enables the synthesis of structurally complex amines in moderate‐to‐good isolated yields using biomass‐derived phenols, natural α‐amino acids, and naphthols under remarkably mild reaction conditions. For the photooxygenation of phenols, a novel chrysazine‐based catalyst system was introduced, demonstrating its efficiency for the synthesis of natural products – hallerone, rengyolone, and the pharmaceutically relevant prodrug DHED. Two‐for‐one: Arylamines were obtained from biomass‐derived phenolic substrates and cyclic α‐amino acids by combining photooxidative dearomatization with decarboxylation/azomethine ylide chemistry. A novel organophotocatalytic approach was reported for the synthesis of a wide range of p‐quinols, including natural products and pharmaceutically‐relevant compounds.