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Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
Direct Benzylic Phosphination of Toluenes Enabled by a Heterobimetallic LiN(SiMe3)2/Cs2SO4 System
Junyu Ma1, Yan-En Wang2, Yunfei Gao1
1State Key Laboratory of Materials Oriented Chemical Engineering (MCE), Technical Institute of Fluorochemistry (TIF), School of Chemistry and Molecular Engineering, Nanjing Tech University, 30 South Puzhu Road, Nanjing 211816, P. R. China.
Abstract:
Organophosphorus compounds hold significant importance in materials science, medicinal chemistry, and agrochemicals. However, their syntheses have mainly relied on transition metals and prefunctionalized substrates. To overcome these limitations, we herein report a transition-metal-free, chemoselective benzylic phosphination of toluenes mediated by a heterobimetallic LiN(SiMe3)2/Cs2SO4 system. This protocol directly activates inert benzylic C-H bonds with good functional group tolerance, circumventing the need for substrate prefunctionalizations. The practicality of this method is demonstrated by gram-scale synthesis and further derivatization of the phosphine products.
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