Photocatalyzed Aerobic Dearomatization of Naphthylamines under Visible‐Light Irradiation

Abstract The dearomatization of aromatic substrates via photocatalytic methodologies has gained escalating prominence to access molecular complexity. Although much focus has been put on non‐active arenes, naphthols and N‐based heteroaromatics, arylamines have so far remained in the background. Herein, we report a photocatalytic strategy for the aerobic, dearomative hydroxylation of naphthylamines under visible‐light irradiation. Our investigation highlights singlet oxygen generation as a viable mechanism for aromaticity disruption, mitigating selectivity issues deriving from the direct oxidation of targeted arylamines. Finally, we showcased the synthetic value of the obtained dearomatized products in a late‐stage diversification campaign.