Single-Crystal-to-Single-Crystal Transition in an Enantiopure [7]Helquat Salt: The First Observation of a Reversible Phase Transition in a Helicene-Like Compound.

Here it is reported that crystals of an enantiopure [7]helquat salt undergo reversible thermal solid-solid phase transition at 404 K. Differential scanning calorimetry (DSC), capillary electrophoresis (CE), and X-ray diffraction analysis were used to unravel the mechanistic details of this process. The single-crystal-to-single-crystal course enabled direct monitoring of the structural changes by in situ variable-temperature X-ray diffraction, thus providing the first direct evidence of a solid phase transition in a helicene-like compound.

A new class of organosuperbases, N-alkyl- and N-aryl-1,3-dialkyl-4,5-dimethylimidazol-2-ylidene amines: synthesis, structure, pK(BH+) measurements, and properties.

A series of stable organosuperbases, N-alkyl- and N-aryl-1,3-dialkyl-4,5-dimethylimidazol-2-ylidene amines, were efficiently synthesized from N,N'-dialkylthioureas and 3-hydroxy-2-butanone and their basicities were measured in acetonitrile. The derivatives with tert-alkyl groups on the imino nitrogen were found to be more basic than the tBuP(1) (pyrr) phosphazene base in acetonitrile. The origin of the high basicity of these compounds is discussed. In acetonitrile and in the gas phase, the basicity of the alkylimino derivatives depends on the size of the substituent at the imino group, which influences the degree of aromatization of the imidazole ring, as measured by (13)C NMR chemical shifts or by the calculated ΔNICS(1) aromaticity parameters, as well as on solvation effects. If a wider range of imino-substituents, including electron-acceptor substituents, is treated in the analysis then the influence of aromatization is less predominant and the gas-phase basicity becomes more dependent on the field-inductive effect, polarizability, and resonance effects of the substituent.

Synthesis of blood group A and B (type 2) tetrasaccharides. A strategy with fucosylation at the last stage.

The traditionally used strategy for the synthesis of blood group A and B tetrasaccharides includes 2'-O-fucosylation of lactosamine followed by insertion of an α1-3 linked N-acetylgalactosamine or a galactose moiety. Here, we report the synthesis of 3-aminopropyl glycosides of A (type 2) and B (type 2) tetrasaccharides via an alternative sequence, i.e. α-galactosaminylation (or α-galactosylation) followed by α-fucosylation. This strategy allows us to synthesize fucose-free trisaccharides GalNAcα1-3Galß1-4GlcNAc and Galα1-3Galß1-4GlcNAc, which are promising targets for immunotherapy utilising human natural antibodies against the trisaccharides. The key stage in this scheme was the selective chloroacetylation of the 2'-OH group of ßGal in the intermediate trisaccharides having the second (3-OH) unprotected group.The protocol is suitable for multigram syntheses and its further scaling up.

New lipophilic 2-amino-N,N'-dialkyl-4,5-dimethylimidazolium cations: synthesis, structure, properties, and outstanding thermal stability in alkaline media.

A series of new N,N'-dialkyl-4,5-dimethylimidazolium cations possessing electron-rich 2-imidazolylidene- or phosphoranylidene-amino substituents has been efficiently synthesized from common precursors, N,N'-dialkyl-4,5-dimethylimidazol-2-ylidenes. The new lipophilic salts obtained have been found to be highly stable towards strong alkali under both biphasic and homogeneous conditions. Their exceptional aqueous base resistance, which has hitherto only been seen with peralkylated polyaminophosphazenium cations, may be attributed to three factors: aromatic stabilization, efficient resonance charge delocalization, and steric protection of the exocyclic nitrogen linkage due to bulky lipophilic N-alkyl substituents.