A Brønsted acid catalysed regiodivergent phosphorylation of 2-indolylmethanols with diarylphosphine oxides has been established, which provides a brand-new strategy for accessing highly functionalized phosphorus-containing indoles with structural diversity. Under the catalysis of HOTs·H₂O, 2-indolylmethanols undergo regioselective benzylic phosphorylation at room temperature to afford benzylic site phosphorylated indoles in good to high yields (29 examples, up to 98% yield), while C3-phosphorylated indoles are obtained in the presence of HOTf under heating conditions (16 examples, up to 83% yield). Preliminary mechanistic studies suggest that C3-phosphorylated indoles are possibly obtained partially from direct C3-phosphorylation and dominantly from a tandem benzylic phosphorylation/[1,3]-P migration/isomerization sequence from 2-indolylmethanols. Furthermore, the acidity of the Brønsted acid and the reaction temperature play a vital role in the [1,3]-P migration of benzylic phosphorylated indoles to form C3-phosphorylated indoles. This protocol serves as a good example for regioselective benzylic functionalization of 2-indolylmethanols.

中文翻译：

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布朗斯台德酸催化2-吲哚基甲醇的区域发散性磷酸化反应，以合成苄基位点或C3-磷酸化的吲哚衍生物

建立了布朗斯台德酸催化的2-吲哚基甲醇与二芳基膦氧化物的区域发散性磷酸化，这为获得具有结构多样性的高度官能化的含磷吲哚提供了全新的策略。在HOTs·H ₂的催化下O，2-吲哚基甲醇在室温下进行区域选择性苄基磷酸化，以高至高收率获得苄基位点磷酸化的吲哚（29个实例，最高收率98％），而C3磷酸化的吲哚是在加热条件下在HOTf存在下获得的（ 16个示例，最高收率达83％）。初步的机理研究表明，C3磷酸化的吲哚可能部分得自直接的C3磷酸化作用，而主要来自于串联的苄基磷酸化反应/ [1,3] -P迁移/异构化序列（来自2-吲哚基甲醇）。此外，布朗斯台德酸的酸度和反应温度在苄基磷酸化吲哚的[1,3] -P迁移形成C3-磷酸化的吲哚中起着至关重要的作用。