Boron dipyrromethenes (BODIPYs) are a class of tetracoordinate boron compounds that have attracted considerable interest in recent decades due to their excellent spectroscopic properties and structural versatility, leading to their widespread applications in chemical, biological, pharmaceutical and materials science. However, BODIPYs possessing boron-stereogenic centres in enantioenriched forms are rare and catalytic methodology to enantioselectively prepare a boron-stereogenic BODIPY remains elusive. Here we report a palladium-catalysed protocol for the enantioselective synthesis of boron-stereogenic BODIPYs via a desymmetric intramolecular C–H arylation reaction. This method gives access to a wide range of highly functionalized boron-stereogenic BODIPYs, including six- to nine-membered boron heterocycles, with good to excellent enantioselectivities. The discrimination of the two α C–H bonds of the BODIPY core is enabled by the co-action of steric hindrance and attractive interaction in the catalytic chiral pocket. Photophysical properties, derivatizations and applications in chiral recognition of the obtained chiroptical BODIPYs are investigated. This work enriches the chemical diversity of chiroptical BODIPY dyes.

硼二吡咯亚甲基 (BODIPYs) 是一类四配位硼化合物，由于其优异的光谱性质和结构多样性，近几十年来引起了人们的极大兴趣，从而在化学、生物、制药和材料科学中得到了广泛应用。然而，以对映体富集形式拥有硼立体异构中心的 BODIPY 很少见，并且对映选择性制备硼立体异构 BODIPY 的催化方法仍然难以捉摸。在这里，我们报告了一种钯催化方案，用于通过不对称分子内 C-H 芳基化反应对映选择性合成硼立体 BODIPY。这种方法可以获得范围广泛的高度功能化的硼立体 BODIPY，包括六到九元硼杂环，具有良好到优异的对映选择性。BODIPY 核心的两个 α C-H 键的区分是通过空间位阻和催化手性口袋中的吸引相互作用的共同作用实现的。研究了所获得的手性 BODIPY 的光物理性质、衍生化和在手性识别中的应用。这项工作丰富了手性 BODIPY 染料的化学多样性。