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.

中文翻译：

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可见光照射下萘胺的光催化有氧脱芳构化

通过光催化方法对芳香族底物进行脱芳构化在获取分子复杂性方面日益受到重视。尽管人们对非活性芳烃、萘酚和 N 基杂芳烃给予了很多关注，但迄今为止，芳基胺仍处于幕后。在此，我们报告了在可见光照射下萘胺有氧脱芳羟基化的光催化策略。我们的研究强调，单线态氧的生成是破坏芳香性的一种可行机制，可减轻因目标芳胺直接氧化而产生的选择性问题。最后，我们在后期多样化活动中展示了所获得的脱芳构化产品的合成价值。