Optically active alpha-substituted phenyloxyacetyloxy and aroyloxy phosphonates have been synthesized via catalytic asymmetric hydrogenation of the corresponding prochiral alpha,beta-unsaturated phosphonates using Rh(I)/(R,R)-Me-DuPhos as the catalyst in methanol at 18 degrees C. The asymmetric hydrogenation reaction exhibits excellent enantioselectivity with enantiomeric excesses from 91 t...