Retention of configuration on the oxidative addition of P-H bond to platinum (0) complexes: The first straightforward synthesis of enantiomerically pure P-chiral alkenylphosphinates via palladium-catalyzed stereospecific hydrophosphinylation of alkynes

The oxidative addition of pure (RP)-menthyl phenylphosphinate 1 to a platinum (0) complex proceeds readily with retention of configuration at the chiral phosphorus center which was unambiguously confirmed by an X-ray analysis. In the presence of a catalytic amount of palladium, the hydrophosphinylation of a variety of alkynes with 1 also takes place stereospecifically, with retention of configuration, affording high yields of the corresponding vinylphosphinates bearing a single chirality at phosphorus. Copyright © 2002 American Chemical Society.