Palladium-Catalyzed Benzylic Phosphorylation of Diarylmethyl Carbonates.

A palladium-catalyzed benzylic substitution of tert-butyl diarylmethyl carbonates with a pinacol-derived H-phosphonate proceeds to deliver the corresponding benzylic phosphorylated products in good yields. Moreover, the asymmetric synthesis is possible via a Pd/( Rp, R'p)-( S)-Mandyphos-catalyzed kinetic resolution-DYKAT (dynamic kinetic asymmetric transformation) sequence, and optically active α-chiral diarylmethylphosphonates are obtained with synthetically useful yields and enantiomeric ratios (up to 50% and 92:8 er).