Herein, a base-promoted C-P(O) bond formation method has been developed for the phosphorylation of polyfluoroarenes through selective C-F bond cleavage. The high selectivity and mild, transition-metal-free conditions of this method underscore its potential for sustainable synthesis applications. This method expands the scope of polyfluoroarene functionalization, providing a valuable tool for incorporating phosphorus motifs in complex aromatic frameworks.
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