Meng Yan-Dong, Fang Wei, Pei Zheng-Hao, Chen Wen-Hao, Ding Shu-Ying, Shen Meng-Lan, Bu Yingcui, Yao Chuan-Zhi, Li Qiankun, Yu Jie, Jiang Hua-Jie
Department of Applied Chemistry, Anhui Province Engineering Laboratory for Green Pesticide Development and Application, and Anhui Province Key Laboratory of Crop Integrated Pest Management, Anhui Agricultural University, Hefei 230036, China.
JACS Au. 2025 Apr 2;5(4):1965-1973. doi: 10.1021/jacsau.5c00196. eCollection 2025 Apr 28.
The precise construction of boron stereogenic centers represents a significant, yet challenging frontier in asymmetric catalysis, garnering growing attention in recent years. However, feasible catalysis has primarily been limited to transition-metal-catalyzed desymmetrization of pro-chiral BODIPY molecules, while enantioselective synthesis via organocatalysis remains unexplored. Herein, we achieve an organocatalyzed C-N bond-forming SNAr reaction of 3,5-dihalogen BODIPYs via phase-transfer catalysis, enabling the efficient synthesis of a broad range of boron-stereogenic BODIPYs with excellent enantioselectivities (>40 examples, up to 99% ee). The significance and potential of this catalytic approach are further underscored by the versatile applications of enantioenriched 3-amide BODIPYs in asymmetric synthesis, optical activity regulation, bioimaging, and sensing, promoting the development of boron-stereogenic fluorophores.
硼立体中心的精确构建是不对称催化领域一个重要但具有挑战性的前沿课题，近年来受到越来越多的关注。然而，可行的催化主要局限于前手性BODIPY分子的过渡金属催化去对称化反应，而通过有机催化的对映选择性合成仍未得到探索。在此，我们通过相转移催化实现了3,5-二卤代BODIPY的有机催化C-N键形成SNAr反应，能够高效合成多种具有优异对映选择性的硼立体中心BODIPY（>40个实例，高达99% ee）。对映体富集的3-酰胺基BODIPY在不对称合成、光学活性调控、生物成像和传感等方面的广泛应用进一步突出了这种催化方法的重要性和潜力，推动了硼立体中心荧光团的发展。
