Regioselective borylation of (hetero)arenes under mild conditions is an appealing strategy for constructing boron-containing compounds, particularly considering their broad applications in organic synthesis, medicinal chemistry and material science. In this manuscript, we developed a Fe(OTf)₃-promoted, DG (directing group)-controlled, regioselective electrophilic C–H borylation of 2-arylphenolic compounds with BBr₃ at room temperature. C2′-borylation was dramatically accelerated by an LA-catalyst, affording DAOB (diaryloxaborin) with a broad substrate scope in moderate-to-excellent yields. The selective ortho-borylation was successfully achieved by introducing phenolic carbamate as a directing group to overcome the competing Fries rearrangement, giving desired 2-HAB ((2-hydroxyaryl)boronic acid) in good yields for most substrates.

中文翻译：

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室温下 2-芳基酚类化合物的定向基团控制区域选择性 C-H 硼基化


在温和条件下（杂）芳烃的区域选择性硼化是构建含硼化合物的一种有吸引力的策略，特别是考虑到它们在有机合成、药物化学和材料科学中的广泛应用。在这篇手稿中，我们开发了一种 Fe(OTf) ₃ 促进、DG（导向基团）控制、区域选择性亲电 C-H 2-芳基酚化合物与 BBr ₃ 的硼基化反应，反应温度为室内温度。 LA 催化剂极大地加速了 C2'-硼基化，提供了具有广泛底物范围的 DAOB（二芳基恶硼啉），产率中等至优异。通过引入酚氨基甲酸酯作为导向基团以克服竞争性 Fries 重排，成功实现了选择性邻硼酸化，从而对大多数底物以良好的产率产生了所需的 2-HAB（（2-羟基芳基）硼酸）。