Heteropolyacid-Catalyzed Phosphorylation of Secondary Aromatic Alcohols with H-Phosphine Oxides in DMC: A Simple Protocol for C-P Bond Formation.

We successfully achieved the phosphorylation of secondary aromatic alcohols with H-phosphine oxides (less developed system) using phosphotungstic acid as a catalyst in dimethyl carbonate. The system was simple and environmentally friendly and showed better activity than traditional Lewis or Brønsted acids such as FeCl 3 , p -TsOH·H 2 O, etc., generating up to a 97% isolated yield. Control experiments indicated that the reaction did not occur through the radical pathway, and ethers and carbocation were the key intermediates in the pathway.