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

Comprehensive Summary Fluorinated organophosphorus compounds are highly valuable in transition‐metal catalysis and medicinal chemistry. Despite their significance, synthetic methods through catalytic hydrophosphination of β‐CF 3 ‐1,3‐enynes remain unexplored, particularly for divergent synthesis of structurally distinct phosphine derivatives. Herein, we report a copper‐catalyzed divergent hydrophosphination of β‐CF 3 ‐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 CF 3 group and ligands play crucial roles in controlling reactivity and chemoselectivity.