Spatial arrangements of cyclodextrin host-guest complexes in solution studied by 13C NMR and molecular modelling.

13C NMR spectroscopic analyses of Cs symmetric guest molecules in the cyclodextrin host cavity, combined with molecular modelling and solid-state X-ray analysis, provides a detailed description of the spatial arrangement of cyclodextrin host-guest complexes in solution. The chiral cavity of the cyclodextrin molecule creates an anisotropic environment for the guest molecule resulting in a splitting of its prochiral carbon signals in 13C NMR spectra. This signal split can be correlated to the distance of the guest atoms from the wall of the host cavity and to the spatial separation of binding sites preferred by pairs of prochiral carbon atoms. These measurements complement traditional solid-state analyses, which rely on the crystallization of host-guest complexes and their crystallographic analysis.

Preparation of 6-Monohalo-ß-cyclodextrin Derivatives with Selectively Methylated Rims via Diazonium Salts.

A series of 6-monohalo (Cl, Br, and I) ß-cyclodextrin derivatives with various types of methylations were synthesized via a diazotization/nucleophilic displacement reaction from the corresponding methylated cyclodextrin amines. All four starting compounds (6A-amino-6A-deoxy derivatives of native ß-CD, per-6-O-methyl-, per-2,3-O-methyl-, and per-2,3,6-O-methyl-ß-CD) were found to have different reactivities under the same reaction conditions. Unsubstituted and fully per-O-methylated cyclodextrin amines undergo fast transformation, giving lower yields of the monohalogenated product. The selectively methylated cyclodextrin amines react remarkably slower and provide almost complete conversion into the desired monohalogenated compound. A pure product was, in several cases, successfully isolated with simple purification techniques (extraction and precipitation), allowing large-scale preparations. This new method opens the way for preparing poorly investigated monofunctionalized selectively methylated cyclodextrins.

Preparation of ß-cyclodextrin-based dimers with selectively methylated rims and their use for solubilization of tetracene.

A series of ß-cyclodextrin dimers selectively permethylated on the primary or secondary rim with two different types of spacers have been synthesized effectively utilizing conventional and newly developed methods. Their structure analyses by 1H NMR and NOESY NMR imply the dependence of molecular symmetry on the type of spacer. The ability of synthesized dimers to increase the solubility of tetracene in DMSO was evaluated and compared to native cyclodextrins and their methylated derivatives. The newly synthesized compounds expressed better effectiveness than other tested supramolecular hosts.