Application of Green Chiral Chromatography in Enantioseparation of Newly Synthesized Racemic Marinoepoxides
Enantioseparation of the newly synthesized series of novel quinoline-2(1<i>H</i>)-one epoxide structures <i>rac</i>-<b>6a</b>–<b>c</b> and <i>rac</i>-<b>8a</b>–<b>c</b>, named marinoepoxides, is described. Marinoepox...
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| Format: | Article |
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MDPI AG
2022-08-01
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| Series: | Marine Drugs |
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| Online Access: | https://www.mdpi.com/1660-3397/20/8/530 |
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| author | Anđela Buljan Marin Roje |
| author_facet | Anđela Buljan Marin Roje |
| author_sort | Anđela Buljan |
| collection | DOAJ |
| description | Enantioseparation of the newly synthesized series of novel quinoline-2(1<i>H</i>)-one epoxide structures <i>rac</i>-<b>6a</b>–<b>c</b> and <i>rac</i>-<b>8a</b>–<b>c</b>, named marinoepoxides, is described. Marinoepoxide <i>rac</i>-<b>6a</b>, 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 <b>5</b> or <b>7</b>, to the carbon-oxygen double bond of the corresponding quinoline-2(1<i>H</i>)-one-4-carbaldehyde <b>4a</b>–<b>c</b> in good yield. Separation of enantiomers of (±)-2,3,3-trisubstituted marinoepoxides <i>rac</i>-<b>6a</b>–<b>c</b> and (±)-<i>trans</i>-2,3-disubstituted marinoepoxides <i>rac</i>-<b>8a</b>–<b>c</b> was studied using two immobilized polysaccharide type chiral stationary phases (CSPs); <i>tris</i>-(3,5-dichlorophenylcarbamoyl)cellulose stationary phase (CHIRAL ART Cellulose-SC) and <i>tris-</i>(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 <i>n</i>-hexane/ethanol (80/20, <i>v</i>/<i>v</i>) as mobile phase, and by supercritical fluid chromatography (SFC) using CO<sub>2</sub>/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. |
| first_indexed | 2024-03-09T04:10:30Z |
| format | Article |
| id | doaj.art-38cbc17ff57a403aa689fc9ecd5d3c6a |
| institution | Directory Open Access Journal |
| issn | 1660-3397 |
| language | English |
| last_indexed | 2024-03-09T04:10:30Z |
| publishDate | 2022-08-01 |
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| series | Marine Drugs |
| spelling | doaj.art-38cbc17ff57a403aa689fc9ecd5d3c6a2023-12-03T14:00:42ZengMDPI AGMarine Drugs1660-33972022-08-0120853010.3390/md20080530Application of Green Chiral Chromatography in Enantioseparation of Newly Synthesized Racemic MarinoepoxidesAnđela Buljan0Marin Roje1Ruđer Bošković Institute, Department of Organic Chemistry and Biochemistry, Laboratory for Chiral Technologies, Bijenička cesta 54, 10 000 Zagreb, CroatiaRuđer Bošković Institute, Department of Organic Chemistry and Biochemistry, Laboratory for Chiral Technologies, Bijenička cesta 54, 10 000 Zagreb, CroatiaEnantioseparation of the newly synthesized series of novel quinoline-2(1<i>H</i>)-one epoxide structures <i>rac</i>-<b>6a</b>–<b>c</b> and <i>rac</i>-<b>8a</b>–<b>c</b>, named marinoepoxides, is described. Marinoepoxide <i>rac</i>-<b>6a</b>, 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 <b>5</b> or <b>7</b>, to the carbon-oxygen double bond of the corresponding quinoline-2(1<i>H</i>)-one-4-carbaldehyde <b>4a</b>–<b>c</b> in good yield. Separation of enantiomers of (±)-2,3,3-trisubstituted marinoepoxides <i>rac</i>-<b>6a</b>–<b>c</b> and (±)-<i>trans</i>-2,3-disubstituted marinoepoxides <i>rac</i>-<b>8a</b>–<b>c</b> was studied using two immobilized polysaccharide type chiral stationary phases (CSPs); <i>tris</i>-(3,5-dichlorophenylcarbamoyl)cellulose stationary phase (CHIRAL ART Cellulose-SC) and <i>tris-</i>(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 <i>n</i>-hexane/ethanol (80/20, <i>v</i>/<i>v</i>) as mobile phase, and by supercritical fluid chromatography (SFC) using CO<sub>2</sub>/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.https://www.mdpi.com/1660-3397/20/8/530green solventschiral chromatographymarinoepoxidesmarinoaziridines2,3-disubstituted epoxides2,3,3-trisubstituted epoxides |
| spellingShingle | Anđela Buljan Marin Roje Application of Green Chiral Chromatography in Enantioseparation of Newly Synthesized Racemic Marinoepoxides Marine Drugs green solvents chiral chromatography marinoepoxides marinoaziridines 2,3-disubstituted epoxides 2,3,3-trisubstituted epoxides |
| title | Application of Green Chiral Chromatography in Enantioseparation of Newly Synthesized Racemic Marinoepoxides |
| title_full | Application of Green Chiral Chromatography in Enantioseparation of Newly Synthesized Racemic Marinoepoxides |
| title_fullStr | Application of Green Chiral Chromatography in Enantioseparation of Newly Synthesized Racemic Marinoepoxides |
| title_full_unstemmed | Application of Green Chiral Chromatography in Enantioseparation of Newly Synthesized Racemic Marinoepoxides |
| title_short | Application of Green Chiral Chromatography in Enantioseparation of Newly Synthesized Racemic Marinoepoxides |
| title_sort | application of green chiral chromatography in enantioseparation of newly synthesized racemic marinoepoxides |
| topic | green solvents chiral chromatography marinoepoxides marinoaziridines 2,3-disubstituted epoxides 2,3,3-trisubstituted epoxides |
| url | https://www.mdpi.com/1660-3397/20/8/530 |
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