Keywords: P-Chiral phosphane oxides / Alkylations / Halides / MetallationsP-Chiral tertiary phosphane oxides have been prepared from each of the secondary phosphane oxides racemic 1, (S P )-(−)-4 and (R P )-(+)-tert-butylphenylphosphane oxide (5) by lithiation with LDA or nBuLi, or sodiation with sodium hydride, in THF, and then by treatment with a series of primary alkyl halides. Doubly P-chiral ditertiary bis(phosphane oxides) are also obtained from these metallated secondary phosphane oxides by treatment with electrophiles based on straight-chain, tartrate-derived, and bishalomethylarene dihalides. In general, the bis-phosphane oxides are obtained in good yields. However, when the α,ω-dihalide bears an em-