Cu-Catalyzed Controllable Single and Double Hydrophosphination of Trifluoromethyl 1,3-Enynes†

Abstract

Fluorinated organophosphorus compounds are highly valuable in transition-metal catalysis and medicinal chemistry. Despite their significance, synthetic methods through catalytic hydrophosphination of β-CF₃-1,3-enynes remain unexplored, particularly for divergent synthesis of structurally distinct phosphine derivatives. Herein, we report a copper-catalyzed divergent hydrophosphination of β-CF₃-1,3-enynes with diarylphosphines. By fine-tuning the copper source, ligand, and base, this protocol enables selective access to fluorinated allenyl monophosphines and dienyl bisphosphines in good to excellent yields with excellent regio- and stereoselectivity. The transformation exhibits broad substrate scope and functional-group tolerance, proceeds under mild conditions, and enables versatile downstream derivatizations. Mechanistic studies indicate that the CF₃ group and ligands play crucial roles in controlling reactivity and chemoselectivity.