Aqueous Flavin Photoredox Catalysis Drives Exclusive C3-Alkylation of Indolyl Radical Cations in Route to Unnatural Tryptophan Mimetics

水相黄素光氧化还原催化驱动吲哚基自由基阳离子的特异性C3-烷基化,从而合成非天然色氨酸类似物

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Abstract

One way to build chemical diversity into indoles is to oxidize them to indolyl radical cations (Ind(•+)). These intermediates can accept new functional groups across C2-C3 bonds or independently at C2. Less encountered is selective diversification at C3, a position plagued by competing dearomative side reactions. We disclose an aqueous photoredox-catalyzed method for transforming Ind(•+) into C3-substituted tryptophan mimetics that uses water as a transient protecting group to guide site-selective C3 alkylation.

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