Chiral β-amidophosphine boranes 7a−f can be diastereoselectively alkylated, using O-protectedamino-alcohols as chiral inducers, to furnish α-substituted β-amidophosphine boranes 8a−f and9−12 with up to 72% diastereoisomeric excess. Selective deprotection afforded optically purecarboxylic derivative 13 which is a key intermediate for the synthesis of various potential chiralligands for asymmetric catalysis.