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Updated: May 22, 2026
![[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
Copper-Catalyzed Enantioselective C-H Phosphorylation Enabled by a 3,3'-Difluorinated BINOL Ligand
Qiang Yue1, Lei Wang1, Hui-Nan Ren1
1State Key Laboratory of Soil Pollution Control and Safety, Department of Chemistry, Zhejiang University, Hangzhou, China.
Abstract:
The asymmetric construction of C-P bonds via transition-metal-catalyzed enantioselective C-H activation remains a significant and unresolved challenge. Herein, we report an unprecedented copper-catalyzed enantioselective C-H phosphorylation through oxidative C-H/P-H coupling. This method employs earth-abundant copper catalyst and readily accessible 3,3'-difluorinated BINOL (1,1'-bi-2-naphthol) ligand, which proved essential for achieving high reactivity and enantioselectivity. A broad range of unmasked H-phosphonates and secondary phosphine oxides (SPOs) serve as practical coupling partners, delivering planar-chiral metallocenes in good yields with high enantioselectivity (up to 99:1 er). The robustness of this approach is demonstrated through gram-scale synthesis, facile directing-group removal, and versatile downstream transformations. Furthermore, the resulting chiral phosphines were applied as a new class of Lewis base catalysts in the enantioselective allylation of aldehydes, underscoring their potential utility in asymmetric synthesis.
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