Shown is the preparation and subsequent elaboration of P-chiral compounds that can be used as a building block for many P-chiral ligands used, for example, in asymmetric catalytic reactions. Specifically, a synthesis is shown for RP(O)(OR*)CH2OH, with R=H, Ph, aryl, alkyl, and R*=menthol (and other chiral alcohol-derived moieties), especially HP(O)(OMen)CH2OH (Men=L-menthol). This versatile building block is easily synthesized via reaction of inexpensive starting materials, H3PO2, menthol as the chiral auxiliary, and paraformaldehyde.