Methods are reported for the attachment of alpha-nucleophiles to the primary and secondary sides of the cyclodextrin cavity. Six new materials have been prepared in which beta CD has been modified by hydrazine, hydroxylamine, oxime, and hydroperoxide functionalities. Transacylating studies with p-NPA have demonstrated that the primary-side hydroxylamine shows the highest reactivity with a 1900-fold increase in rate over beta CD at pH 6.5. Other alpha-nucleophiles show less remarkable rate increases in this system but, in some cases, demonstrate hydrogen-bonding to the cyclodextrin rim and inhibition kinetics.