Stereospecific Synthesis of α- and ß-Hydroxyalkyl P-Stereogenic Phosphine-Boranes and Functionalized Derivatives: Evidence of the P=O Activation in the BH3 -Mediated Reduction.

Access to hydroxy-functionalized P-chiral phosphine-boranes has become an important field in the synthesis of P-stereogenic compounds used as ligands in asymmetric catalysis. A family of optically pure α and ß-hydroxyalkyl tertiary phosphine-boranes has been prepared by using a three-step procedure from readily accessible enantiopure adamantylphosphinate, obtained by semi-preparative HPLC on multigram scale. Firstly, a two-step one-pot transformation affords the enantiopure hydroxyalkyl tertiary phosphine oxides in good yields and enantioselectivities. The third step, BH3 -mediated reduction, allows the formation of the desired phosphine-boranes with excellent stereospecifity. The mechanistic study of this reduction provides new evidence to elucidate the crucial role of the pendant hydroxy group and the subsequent activation of the P=O bond by the boron atom.