Synthetic Study of Natural Metabolites Containing a Benzo[<i>c</i>]oxepine Skeleton: Heterocornol C and D
A versatile strategy for the enantioselective synthesis of a benzo[<i>c</i>]oxepine structural core containing natural secondary metabolites was developed. The key steps of the synthetic approach include ring-closing alkene metathesis for seven-member ring construction, the Suzuki–Miyaur...
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| Format: | Article |
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MDPI AG
2023-06-01
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| Series: | International Journal of Molecular Sciences |
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| Online Access: | https://www.mdpi.com/1422-0067/24/12/10331 |
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| author | Ján Gettler Tomáš Čarný Martin Markovič Peter Koóš Erika Samoľová Ján Moncoľ Tibor Gracza |
| author_facet | Ján Gettler Tomáš Čarný Martin Markovič Peter Koóš Erika Samoľová Ján Moncoľ Tibor Gracza |
| author_sort | Ján Gettler |
| collection | DOAJ |
| description | A versatile strategy for the enantioselective synthesis of a benzo[<i>c</i>]oxepine structural core containing natural secondary metabolites was developed. The key steps of the synthetic approach include ring-closing alkene metathesis for seven-member ring construction, the Suzuki–Miyaura cross-coupling reaction for the installation of the double bond and Katsuki–Sharpless asymmetric epoxidation for the introduction of chiral centers. The first total synthesis and absolute configuration assignment of heterocornol D (<b>3a</b>) were achieved. Four stereoisomers, <b>3a</b>, <i>ent</i>-<b>3a</b>, <b>3b</b> and <i>ent</i>-<b>3b</b>, of this natural polyketide were prepared, starting with 2,6-dihydroxy benzoic acid and divinyl carbinol. The absolute and relative configuration of heterocornol D was assigned via single-crystal X-ray analysis. The extension of the described synthetic approach is further presented with the synthesis of heterocornol C by applying the ether group reduction method to the lactone. |
| first_indexed | 2024-03-11T02:20:20Z |
| format | Article |
| id | doaj.art-5acac42d6707472690948078e0241e1c |
| institution | Directory Open Access Journal |
| issn | 1661-6596 1422-0067 |
| language | English |
| last_indexed | 2024-03-11T02:20:20Z |
| publishDate | 2023-06-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | International Journal of Molecular Sciences |
| spelling | doaj.art-5acac42d6707472690948078e0241e1c2023-11-18T10:52:02ZengMDPI AGInternational Journal of Molecular Sciences1661-65961422-00672023-06-0124121033110.3390/ijms241210331Synthetic Study of Natural Metabolites Containing a Benzo[<i>c</i>]oxepine Skeleton: Heterocornol C and DJán Gettler0Tomáš Čarný1Martin Markovič2Peter Koóš3Erika Samoľová4Ján Moncoľ5Tibor Gracza6Department of Organic Chemistry, Institute of Organic Chemistry, Catalysis and Petrochemistry, Slovak University of Technology, Radlinského 9, SK-812 37 Bratislava, SlovakiaDepartment of Organic Chemistry, Institute of Organic Chemistry, Catalysis and Petrochemistry, Slovak University of Technology, Radlinského 9, SK-812 37 Bratislava, SlovakiaDepartment of Organic Chemistry, Institute of Organic Chemistry, Catalysis and Petrochemistry, Slovak University of Technology, Radlinského 9, SK-812 37 Bratislava, SlovakiaDepartment of Organic Chemistry, Institute of Organic Chemistry, Catalysis and Petrochemistry, Slovak University of Technology, Radlinského 9, SK-812 37 Bratislava, SlovakiaInstitute of Physics of the Czech Academy of Science, Na Slovance 2, 182 21 Prague, Czech RepublicDepartment of Inorganic Chemistry, Institute of Inorganic Chemistry, Technology and Materials, Slovak University of Technology, Radlinského 9, SK-812 37 Bratislava, SlovakiaDepartment of Organic Chemistry, Institute of Organic Chemistry, Catalysis and Petrochemistry, Slovak University of Technology, Radlinského 9, SK-812 37 Bratislava, SlovakiaA versatile strategy for the enantioselective synthesis of a benzo[<i>c</i>]oxepine structural core containing natural secondary metabolites was developed. The key steps of the synthetic approach include ring-closing alkene metathesis for seven-member ring construction, the Suzuki–Miyaura cross-coupling reaction for the installation of the double bond and Katsuki–Sharpless asymmetric epoxidation for the introduction of chiral centers. The first total synthesis and absolute configuration assignment of heterocornol D (<b>3a</b>) were achieved. Four stereoisomers, <b>3a</b>, <i>ent</i>-<b>3a</b>, <b>3b</b> and <i>ent</i>-<b>3b</b>, of this natural polyketide were prepared, starting with 2,6-dihydroxy benzoic acid and divinyl carbinol. The absolute and relative configuration of heterocornol D was assigned via single-crystal X-ray analysis. The extension of the described synthetic approach is further presented with the synthesis of heterocornol C by applying the ether group reduction method to the lactone.https://www.mdpi.com/1422-0067/24/12/10331heterocornolpolyketidebenzo[<i>c</i>]oxepin-1-onenatural compoundasymmetric synthesis |
| spellingShingle | Ján Gettler Tomáš Čarný Martin Markovič Peter Koóš Erika Samoľová Ján Moncoľ Tibor Gracza Synthetic Study of Natural Metabolites Containing a Benzo[<i>c</i>]oxepine Skeleton: Heterocornol C and D International Journal of Molecular Sciences heterocornol polyketide benzo[<i>c</i>]oxepin-1-one natural compound asymmetric synthesis |
| title | Synthetic Study of Natural Metabolites Containing a Benzo[<i>c</i>]oxepine Skeleton: Heterocornol C and D |
| title_full | Synthetic Study of Natural Metabolites Containing a Benzo[<i>c</i>]oxepine Skeleton: Heterocornol C and D |
| title_fullStr | Synthetic Study of Natural Metabolites Containing a Benzo[<i>c</i>]oxepine Skeleton: Heterocornol C and D |
| title_full_unstemmed | Synthetic Study of Natural Metabolites Containing a Benzo[<i>c</i>]oxepine Skeleton: Heterocornol C and D |
| title_short | Synthetic Study of Natural Metabolites Containing a Benzo[<i>c</i>]oxepine Skeleton: Heterocornol C and D |
| title_sort | synthetic study of natural metabolites containing a benzo i c i oxepine skeleton heterocornol c and d |
| topic | heterocornol polyketide benzo[<i>c</i>]oxepin-1-one natural compound asymmetric synthesis |
| url | https://www.mdpi.com/1422-0067/24/12/10331 |
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