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Application of Green Chiral Chromatography in Enantioseparation of Newly Synthesized Racemic Marinoepoxides

Enantioseparation of the newly synthesized series of novel quinoline- 2(1H)-one epoxide structures rac-6a–c and rac-8a–c, named marinoepoxides, is described. Marinoepoxide rac-6a, the key intermediate in the total synthesis of natural products marinoaziridines A and B, as well as their structural analogues, was synthesized by addition of the achiral ylide generated in situ from the sulfonium salt 5 or 7, to the carbon-oxygen double bond of the corresponding quinoline-2(1H)-one-4-carbaldehyde 4a–c in good yield. Separation of enantiomers of (±)-2, 3, 3-trisubstituted marinoepoxides rac-6a–c and (±)-trans-2, 3-disubstituted marinoepoxides rac-8a–c was studied using two immobilized polysaccharide type chiral stationary phases (CSPs) ; tris-(3, 5- dichlorophenylcarbamoyl)cellulose stationary phase (CHIRAL ART Cellulose-SC) and tris-(3, 5-dimethylphenylcarbamoyl)amylose stationary phase (CHIRAL ART Amylose-SA). Enantioseparation conditions were explored by high-performance liquid chromatography (HPLC) using dimethyl carbonate/alcohol mixtures and n-hexane/ethanol (80/20, v/v) as mobile phase, and by supercritical fluid chromatography (SFC) using CO2/alcohol mixtures as mobile phase. In all examined racemates, enantioseparation was successfully achieved, but its efficiency largely depended on the structure of chiral selector and type/composition of the mobile phase.

green solvents ; chiral chromatography ; marinoepoxides ; marinoaziridines ; 2, 3-disubstituted epoxides ; 2, 3, 3-trisubstituted epoxides ; enantioseparation ; supercritical fluid chromatography (SFC) ; high-performance liquid chromatography (HPLC) ; supercritical carbon dioxide ; dimethyl carbonate (DMC)

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