Keywords: Ceramides / Dihydroxylation / Enantioselective synthesis / Fluorine / Sphingolipids Two diastereomeric enantiopure 4-fluoro-4,5-dihydroceramides with the natural D-erythro configuration at the 2-and 3-carbon atoms have been synthesized in an enantioselective eleven-step sequence. The key step of the synthesis was a diastereoselective asymmetric Sharpless dihydroxylation of ethyl trans-4-fluorooctadec-2-enoate (8) with AD-mix-β to afford the D-erythro arrangement. The diastereomers of the other enantiomeric series were synthesized analogously with the use of AD-mix-α. In all cases, the nitrogen heteroatom

Monolayers of enantiomeric compounds as well as diastereomeric mixtures and racemic/diastereomeric mixtures of ethyl 2-azido-4-fluoro-3-hydroxystearates have been investigated using surface pressure-area isotherms and Brewster angle microscopy. All monolayers collapse out of the liquid-expanded phase, forming 3D collapse structures which were visualized with scanning force microscopy. The enantiomeric compound and the diastereomeric mixtures form unique fiber-like network structures with heights between 20 and 40 nm. Interestingly, the shape of the enantiomeric fiber structures is straight, whereas the diastereomeric mixtures exhibit curved fibers of different sizes. The racemic mixture however forms circular 10 nm high and 20-50 microm broad structures. The shape of unconventional collapse structures could be changed by using distinct ratios of diastereomeric or racemic/diastereomeric mixed compounds.

No abstract

γ‐Fluoro‐α, β‐unsaturated carboxylic esters 7a, 7b and 7d and 4‐fluoro‐4‐phenylbut‐3‐enoic ester (8) are obtained by two alternative pathways from 2‐fluoro aldehydes 5a—d, either by Horner—Wadsworth—Emmons reaction or by Wittig reaction. The aldehydes 5a—d are prepared by Swern oxidation of the corresponding fluorohydrins 4a—d. These are available from α‐olefins by bromofluorination, bromineby‐acetate replacement and subsequent hydrolysis.

The phase behavior of enantiomeric compounds as well as mixtures of enantiopure and racemic diastereomers of ethyl 4-fluoro-2,3-dihydroxystearates has been investigated using surface pressure-area isotherms and Brewster angle microscopy (BAM). All mixtures exhibit a small plateau region within the surface pressure-area isotherm at 20 degrees C, whereas the enantiopure compound shows an isotherm behavior similar to that of fatty acids. Corresponding to the film balance measurements, the BAM images demonstrate different shapes of the domains within the coexistence region of the liquid-condensed/liquid-expanded phase. The domain structures of the monolayers were visualized after Langmuir-Blodgett transfer on mica sheets by scanning force microscopy (SFM). From the SFM images it becomes obvious that small crystallites are formed for all investigated compounds; however, their molecular assembly is diverse for different enantiomers. Variations in the phase behavior can be correlated with interactions between the polar molecular moieties and the subphase and altered intermolecular interactions. Molecular modeling calculations were applied to elucidate the structural organization of these intermolecular interactions. Ab initio calculations of the minima conformers of (S,S,R)- and (S,S,S)-ethyl 4-fluoro-2,3-dihydroxystearates have been performed to predict with the HARDPACK program the two-dimensional lattice structure based on the P1 space group. These calculations showed that intermolecular hydrogen bridges are crucial for the interactions within and between the molecules.