Zhan Baoquan, Ren Li-Qing, Zhao Jiayi, Zhang Hua, He Chuan
Key Laboratory of Catalysis and Energy Materials Chemistry of Ministry of Education, Hubei Key Laboratory of Catalysis and Materials Science, School of Chemistry and Materials Science, South-Central Minzu University, Wuhan, Hubei, China.
Shenzhen Grubbs Institute and Department of Chemistry, Shenzhen Key Laboratory of Small Molecule Drug Discovery and Synthesis, Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen, Guangdong, China.
Nat Commun. 2025 Jan 7;16(1):438. doi: 10.1038/s41467-024-55796-5.
3-Amino boron dipyrromethenes (BODIPYs) are a versatile class of fluorophores widely utilized in live cell imaging, photodynamic therapy, and fluorescent materials science. Despite the growing demand for optically active BODIPYs, the synthesis of chiral 3-amino-BODIPYs, particularly the catalytic asymmetric version, remains a challenge. Herein, we report the synthesis of boron-stereogenic 3-amino-BODIPYs via a palladium-catalyzed desymmetric C-N cross-coupling of prochiral 3,5-dihalogen-BODIPYs. This approach features a broad substrate scope, excellent functional group tolerance, high efficiency, and remarkable enantioselectivities, under mild reaction conditions. Further stereospecific formation of chiral 3,5-diamino-BODIPYs, along with an investigation into the photophysical properties of the resulting optical BODIPYs are also explored. This asymmetric protocol not only enriches the chemical space of chiroptical BODIPY dyes but also contributes to the realm of chiral boron chemistry.
3-氨基硼二吡咯亚甲基（BODIPY）是一类用途广泛的荧光团，在活细胞成像、光动力疗法和荧光材料科学中得到广泛应用。尽管对具有光学活性的BODIPY的需求不断增长，但手性3-氨基-BODIPY的合成，尤其是催化不对称合成，仍然是一个挑战。在此，我们报道了通过钯催化前手性3,5-二卤代-BODIPY的去对称C-N交叉偶联反应合成硼立体中心的3-氨基-BODIPY。该方法具有底物范围广、官能团耐受性好、效率高以及在温和反应条件下具有显著对映选择性等特点。还探索了手性3,5-二氨基-BODIPY的进一步立体特异性形成，以及对所得光学活性BODIPY的光物理性质的研究。这种不对称方法不仅丰富了手性光学BODIPY染料的化学空间，也为手性硼化学领域做出了贡献。
