Enones are privileged structural motifs in bioactive natural products and pharmaceuticals, but the γ-hydroxylation of enones is challenging. Here we show a mild and efficient method for the direct C(sp³)–H hydroxylation of enones via visible-light-induced hydrogen-atom transfer (HAT), which facilitates γ-hydroxylation of primary, secondary, and tertiary C–H bonds of different enones without involving metal and peroxide. The mechanism study shows that Na₂-eosin Y serves as both the photocatalyst and the source of catalytic bromine radical species in the HAT-based catalytic cycle, and finally sacrifices itself completely by oxidative degradation to produce bromine radical and a major product phthalic anhydride in an environmentally friendly way. This scalable method was demonstrated by plenty of substrates (41 examples) including 10 clinical drugs and 15 natural products to be useful for the late-stage functionalization of enone-containing compounds, and, in particular, has potential application in industry for large-scale production.

烯酮是具有生物活性的天然产物和药物中的特殊结构基序，但烯酮的 γ-羟基化具有挑战性。在这里，我们展示了一种温和有效的方法，通过可见光诱导的氢原子转移 (HAT) 对烯酮进行直接C(sp ³ )-H 羟基化，促进伯、仲和叔 C-H 的 γ-羟基化不涉及金属和过氧化物的不同烯酮键。机理研究表明Na ₂-eosin Y 在基于 HAT 的催化循环中作为光催化剂和催化溴自由基物种的来源，最终通过氧化降解完全牺牲自身，以环境友好的方式产生溴自由基和主要产物邻苯二甲酸酐。这种可扩展的方法被大量底物（41 个例子）证明，包括 10 种临床药物和 15 种天然产物，可用于含烯酮化合物的后期功能化，特别是在工业上具有大规模应用的潜力生产。