Ren Li-Qing, Zhan Baoquan, Zhao Jiayi, Guo Yonghong, Zu Bing, Li Yingzi, He Chuan
Shenzhen Grubbs Institute and Department of Chemistry, Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen, China.
Nat Chem. 2025 Jan;17(1):83-91. doi: 10.1038/s41557-024-01649-z. Epub 2024 Sep 20.
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.
硼二吡咯亚甲基（BODIPY）是一些最受欢迎且不可或缺的四配位硼化合物，由于其优异的光谱和光物理性质而得到了广泛应用。具有硼立体中心的BODIPY很少见，合成具有结构多样性的对映体富集硼立体中心BODIPY的策略仍未充分发展。理论上，BODIPY核心骨架有几个位点可以用不同的取代基进行修饰。然而，由于缺乏通用且高效的不对称合成方法，这种手性BODIPY的潜在多样性尚未得到开发。在此，我们展示了一种模块化的对映选择性组装方法，能够高效地合成多取代硼立体中心BODIPY，且对映选择性优异。成功的关键是钯催化的去对称铃木交叉偶联反应，它能够精确区分设计的前手性BODIPY支架的两个α C-Cl键，从而获得多种高度官能化的硼立体中心BODIPY。我们还进一步探索了所得光学活性BODIPY的衍生化、光物理性质及其在手性识别中的应用。
