Boron dipyrromethenes (BODIPYs) are some of the most popular and indispensable tetracoordinate boron compounds and have found widespread applications owing to their excellent spectroscopic and photophysical properties. BODIPYs possessing boron-stereogenic centres are scarce, and strategies for the synthesis of enantioenriched boron-stereogenic BODIPYs with structural diversity remain underdeveloped. In theory, the BODIPY core skeleton has several sites that could be decorated with different substituents. However, due to the lack of general and efficient asymmetric synthetic methods, this potential diversity of chiral BODIPYs has not been exploited. Here we demonstrate a modular enantioselective assembly of multi-substituted boron-stereogenic BODIPYs in high efficiency with excellent enantioselectivities. Key to the success is the Pd-catalysed desymmetric Suzuki cross-coupling, enabling the precise discrimination of the two α C–Cl bonds of the designed prochiral BODIPY scaffold, giving access to a wide range of highly functionalized boron-stereogenic BODIPYs. Derivatizations, photophysical properties and applications in chiral recognition of the obtained optical BODIPYs are further explored.

二吡咯亚甲基硼（BODIPY）是最流行且不可或缺的四配位硼化合物之一，由于其优异的光谱和光物理性质而得到了广泛的应用。具有硼立体中心的 BODIPY 很稀缺，并且具有结构多样性的对映体富集的硼立体 BODIPY 的合成策略仍然不发达。理论上，BODIPY核心骨架有几个可以用不同取代基修饰的位点。然而，由于缺乏通用且有效的不对称合成方法，手性 BODIPY 的这种潜在多样性尚未得到开发。在这里，我们展示了多取代硼立体 BODIPY 的模块化对映选择性组装，高效且具有优异的对映选择性。成功的关键是 Pd 催化的不对称 Suzuki 交叉偶联，能够精确区分所设计的前手性 BODIPY 支架的两个 α C-Cl 键，从而获得各种高度功能化的硼立体 BODIPY。进一步探讨了所获得的光学 BODIPY 的衍生化、光物理性质以及在手性识别中的应用。