Ma Juan, Guo Luying, Zhang Xue-Qing, Tang Wan-Wan, Guo Xing, Kang Zhengxin, Jiao Lijuan, Hao Erhong, Li Zhong-Yuan
Anhui Laboratory of Molecule-Based Materials, Key Laboratory of Functional Molecular Solids, Ministry of Education, School of Chemistry and Materials Science, Anhui Normal University, Wuhu 241002, China.
JACS Au. 2025 May 16;5(6):2837-2848. doi: 10.1021/jacsau.5c00425. eCollection 2025 Jun 23.
Boron-stereogenic formyl boron dipyrromethene dyes (BODIPYs) have shown notable potential as chiral fluorescent sensors to recognize amino acid enantiomers owing to their remarkable photophysical properties. However, the catalytic asymmetric synthesis of boron-stereogenic formyl BODIPYs remains challenging due to the lack of efficient strategies. Herein, we report an organocatalytic approach by utilizing -heterocyclic carbene (NHC) catalysis to achieve enantioselective esterification, enabling the construction of boron-stereogenic formyl BODIPYs in moderate to good yields with excellent stereoselectivity. The formyl group in these boron-stereogenic BODIPYs serves as a multifunctional handle, facilitating diverse postsynthetic modifications and endowing them with promising applications in chiral recognition. Importantly, the achieved enantiopure BODIPYs exhibit moderate photophysical properties in circular dichroism (CD) and circularly polarized luminescence (CPL) spectra. Furthermore, the enantioselective fluorescent recognition of cysteine and diaminocyclohexane enantiomers by using - reveals their great potential as chiral probes. This study not only offers a practical and environmentally friendly approach to access boron-stereogenic BODIPYs but also underscores their potential applications as chiral fluorescent sensors.
硼立体中心甲酰基硼二吡咯亚甲基染料（BODIPY）由于其卓越的光物理性质，作为识别氨基酸对映体的手性荧光传感器展现出显著潜力。然而，由于缺乏有效的策略，硼立体中心甲酰基BODIPY的催化不对称合成仍然具有挑战性。在此，我们报道了一种利用氮杂环卡宾（NHC）催化实现对映选择性酯化的有机催化方法，能够以中等至良好的产率和优异的立体选择性构建硼立体中心甲酰基BODIPY。这些硼立体中心BODIPY中的甲酰基作为多功能基团，便于进行多种合成后修饰，并赋予它们在手性识别方面的潜在应用前景。重要的是，所获得的对映体纯BODIPY在圆二色性（CD）和圆偏振发光（CPL）光谱中表现出适度的光物理性质。此外，利用 - 对半胱氨酸和二氨基环己烷对映体的对映选择性荧光识别揭示了它们作为手性探针的巨大潜力。这项研究不仅提供了一种实用且环境友好的方法来获得硼立体中心BODIPY，还强调了它们作为手性荧光传感器的潜在应用。
