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Starting with 3,4‐O‐[(R)‐2,2,2‐trichloroethylidene]‐1,2‐O‐isopropylidene‐β‐D‐tagatopyranose 2 obtained from 1,2‐O‐isopropylidene‐β‐D‐fructopyranose 1 by a non‐classical one‐step acetalization with chloral/DCC, the fluoroalkylated glycosyl donors 15 and 17 were synthesised in 3–4 steps. By this sequence, one stereogenic center was inverted, one new chiral center was introduced, and one stereogenic center, for the time being eliminated, was later re‐introduced. The glycals 11 and 12, key intermediates of the synthesis sequence, were accessible from triflate precursors (e.g., 10) by treatment with DBU. Corresponding halogeno‐(6, 7), tosyl‐(5, 8), or mesyl‐(9) precursors were unsuitable. The stereoselective introduction of a chlorodifluoromethyl group was realised by dithionite‐mediated CF2ClBr‐addition to the glycal double bond. Subsequently, either the chlorodifluoromethylated glycosyl bromide (13) or the corresponding pyranoses (14 and 16) were isolated. The latter were still acetylated to the 1‐O...

New perfluoroalkylated amphiphiles based on carbohydrates (D-xylose, D-ribose, D-glucose) and on myo-inositol were synthesized and their thermotropic liquid crystalline behaviour was investigated. The introduction of perfluoroalkyl groups was carried out by radical addition of 1-iodoperfluoroalkanes to O- and C-allyl-substituted sugar and inositol derivatives.

This mini‐review summarizes the knowledge about the scope and pathway of a novel non‐conventional tandem procedure of acetalization which allows a simultaneous epimerization of cyclic polyols with three or four contiguous hydroxyl groups. Such triols and tetrols, e.g., pyranosides or inositols, form acetols on heating with highly active aldehydes or ketones in the presence of a carbodiimide, provided that their OH‐groups show a cis/trans or cis/trans/trans sequence. The inversion of one chiral center (triols) and of one or two chiral centers (tetrols) was achieved. The stepwise removing of the protecting groups is reported. †Dedicated to Prof. Dr. Gerard Descotes on the occasion of his 70th birthday.

The thermal properties of twelve 'single-tailed' carbohydrate-based liquid crystal materials which have a perfluoroalkyl chain (n-C4F9, n-C6F13, n-C8F17) linked to the polar sugar head group are described. All reported amphiphiles, the 6-deoxy-6-C-perfluorohexyl-L-altrose 1, the (5R)-xylopentoses 2, 3 and 4, the 5,6-dideoxy-6-C-perfluoroalkyl-D-glucofuranoses 5 and 6, the 2,3-O-perfluoroalkylidene-D-gulopyranoses 7, 8 and 9 and the 3,4-O-perfluoroalkylidene- D-altropyranoses 10 and 11 form mesophases of the smectic A type. Even a C4F9-chain (compounds 2, 7, and 10) is long enough to cause liquid crystalline behaviour.

Methyl β-D-arabinopyranoside (1), phenyl 1-thio-β-D-galactopyranoside (3), methyl β-L-fucopyranoside (7), methyl β-L-fucopyranoside (9), 1,6-anhydro-β-D-galactopyranoside (D-galactosan; 11), and 1,6-anhydro-β-D-mannopyranoside (D-mannosan; 14) were stereospecifically converted in moderate up to good yields into methyl 4-O-cyclohexylcarbamoyl-2,3-O-(2,2,2-trichloroethylidene)-β-D-lyxopyranoside (2), phenyl 4-(9-cyclohexyIcarbamoyl-6-O-formyl-2,3-O-(2,2,2-trichloroethylidene)-1-thio-β-D-gulopyranoside (4) / phenyl 4-O-cyclohexylcarbamoyl-2,3-O-(2,2,2-trichloroethylidene)-1-thio-β-D-gulopyraoside (5), methyl 4-O-cyclohexylcarbamoyl-2,3-O-(2,2,2-trichloroethylidene)-6-deoxy-α-L-gulopyranoside (8), methyl 2,3-O-(2,2,2-trichloroethylidene)-4-O-cyclohexylcarbamoyl-6-deoxy-β-L-gulopyranoside (10), 1,6-anhydro-4-O-cyclohexyl-carbamoyl-2,3-O-(2,2,2-trichloroethylidene)-β-D-gulopyranoside (12), and 1,6-anhydro-2-O-cyclohexylcarbamoyl-3,4-O-(2,2,2-trichloroethylidene)-β-D-altropyranoside (15), respectively, ...

The geminally C-branched 6,6-di-C-n-alkyl-d-galactopyranoses 3a–d prepared in two steps from 1,2:3,4-di-O-isopropylidene-d-galacturonic acid methylester 1 and the even numbered C8-C12-alkylmagnesium bromides, represent a new group of ‘double tailed’ thermotropic mesogens forming columnar supramolecular structures based on hydrogen bridged (disc-like) multimers in accordance with the hypothesis of the Praefcke group. Furthermore, the thermal behaviour of the homologous 6-O-alkyl-d-galactopyranoses 4a–e is discussed in connection with the revised model for the molecular arrangement in smectic A phases of ‘single tailed’ carbohydrates.