alpha-Cyclodextrins (alpha-CDs) containing "PPh" units which cap the primary face of the CD were obtained in high yield by reaction of Li(2)PPh with A,B- or A,C-dimesylated and A,B,D,E-tetramesylated precursors; the resulting phosphines are diastereomerically pure and constitute valuable precursors for the synthesis of metallo-cavitands.