title: Selective Secondary Face Modification of Cyclodextrins by Mechanosynthesis.
abstract: 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, N-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 (1)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.
authors.affiliation: †Unité de Catalyse et de Chimie du Solide - UCCS, CNRS UMR 8181, Université d'Artois, Faculté des Sciences Jean Perrin, SP18, 62307 Lens Cedex, France.
authors.forename: Stéphane
authors.initials: S
authors.lastname: Menuel
authors.affiliation: ‡Fédération M.E. Chevreul, CNRS FR2638, Université de Lille, Cité Scientifique, Bâtiment C4 - BP 90108, 59652 Villeneuve d'Ascq Cedex, France.
authors.forename: Bertrand
authors.initials: B
authors.lastname: Doumert
authors.affiliation: †Unité de Catalyse et de Chimie du Solide - UCCS, CNRS UMR 8181, Université d'Artois, Faculté des Sciences Jean Perrin, SP18, 62307 Lens Cedex, France.
authors.forename: Sébastien
authors.initials: S
authors.lastname: Saitzek
authors.affiliation: †Unité de Catalyse et de Chimie du Solide - UCCS, CNRS UMR 8181, Université d'Artois, Faculté des Sciences Jean Perrin, SP18, 62307 Lens Cedex, France.
authors.forename: Anne
authors.initials: A
authors.lastname: Ponchel
authors.affiliation: §Unité de Catalyse et de Chimie du Solide - UCCS, CNRS UMR 8181, Ecole Nationale Supérieure de Chimie de Lille, Université de Lille, Cité Scientifique, Bâtiment C7 - BP 90108, 59652 Villeneuve d'Ascq Cedex, France.
authors.forename: Laurent
authors.initials: L
authors.lastname: Delevoye
authors.affiliation: †Unité de Catalyse et de Chimie du Solide - UCCS, CNRS UMR 8181, Université d'Artois, Faculté des Sciences Jean Perrin, SP18, 62307 Lens Cedex, France.
authors.forename: Eric
authors.initials: E
authors.lastname: Monflier
authors.affiliation: †Unité de Catalyse et de Chimie du Solide - UCCS, CNRS UMR 8181, Université d'Artois, Faculté des Sciences Jean Perrin, SP18, 62307 Lens Cedex, France.
authors.forename: Frédéric
authors.initials: F
authors.lastname: Hapiot