α-,
β-, and γ-cyclodextrins (CDs) were modified
on their secondary face by mechanosynthesis at room temperature using
a laboratory-scale ball-mill. Mono-2-tosylated α-, β-,
and γ-CDs were obtained in good yield from mixtures of native
α-, β-, and γ-CDs, respectively, <i>N</i>-tosylimidazole, and an inorganic base, with each of them being in
the solid state. The yields appeared to be dependent upon the nature
of the base and the reaction time. A kinetic monitoring by <sup>1</sup>H NMR spectroscopy demonstrated that the highest yields in mono-2-tosyl-CDs
were measured using KOH as a base in very short reaction times (up
to 65% in 80 s). Mono-(2,3-manno-epoxide) α-, β-, and
γ-CDs were subsequently synthesized by ball-milling a mixture
of monotosylated α-, β-, and γ-CDs, respectively,
and KOH. The characterization of the modified CDs was carried out
by X-ray diffraction, mass spectrometry, solid-state NMR, and diffuse
reflectance UV–vis (DR UV–vis) spectroscopies. Clues
to the supramolecular arrangement of the molecules in the solid state
provide information on the reaction mechanism
