Preassociating α-nucleophiles based on β-cyclodextrin. Their synthesis and reactivity

Article abstract of DOI:10.1021/ja00147a005

Methods are reported for the attachment of α-nucleophiles to the primary and secondary sides of the cyclodextrin cavity. Six new materials have been prepared in which βCD 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 βCD at pH 6.5. Other α-nucleophiles show less remarkable rate increases in this system but, in some cases, demonstrate hydrogen-bonding to the cyclodextrin rim and inhibition kinetics.