Synthesis of Natural (−)-Antrocin and Its Enantiomer via Stereoselective Aldol Reaction
The total synthesis of (−)-antrocin and its enantiomer are presented. Antrocin (−)-<b>1</b> is an important natural product which acts as an antiproliferative agent in a metastatic breast cancer cell line (IC<sub>50</sub>: 0.6 <i>μ</i>...
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MDPI AG
2020-02-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/25/4/831 |
| _version_ | 1819040820591853568 |
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| author | Venkatachalam Angamuthu Dar-Fu Tai |
| author_facet | Venkatachalam Angamuthu Dar-Fu Tai |
| author_sort | Venkatachalam Angamuthu |
| collection | DOAJ |
| description | The total synthesis of (−)-antrocin and its enantiomer are presented. Antrocin (−)-<b>1</b> is an important natural product which acts as an antiproliferative agent in a metastatic breast cancer cell line (IC<sub>50</sub>: 0.6 <i>μ</i>M). The key features of this synthesis are: (a) selective anti-addition of trimethylsilyl cyanide (TMSCN) to <i>α,β</i>-unsaturated ketone; (b) resolution of (±)<b>-7</b> using chiral auxiliary L-dimethyl tartrate through formation of cyclic ketal diastereomers followed by simple column chromatography separation and acid hydrolysis; (c) substrate-controlled stereoselective aldol condensation of (+)-<b>12</b> with monomeric formaldehyde and pyridinium chlorochromate (PCC) oxidation for synthesis of essential lactone core in (−)-<b>14</b>; and (d) non-basic Lombardo olefination of the carbonyl at the final step to yield (−)-antrocin. In addition, (+)<b>-9</b> cyclic ketal diastereomer was converted to (+)-antrocin with similar reaction sequences. |
| first_indexed | 2024-12-21T09:15:11Z |
| format | Article |
| id | doaj.art-e7a390107edc491b8c170af54a350211 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-12-21T09:15:11Z |
| publishDate | 2020-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-e7a390107edc491b8c170af54a3502112022-12-21T19:09:09ZengMDPI AGMolecules1420-30492020-02-0125483110.3390/molecules25040831molecules25040831Synthesis of Natural (−)-Antrocin and Its Enantiomer via Stereoselective Aldol ReactionVenkatachalam Angamuthu0Dar-Fu Tai1Department of Chemistry, Pondicherry University, Puducherry 605014, IndiaDepartment of Chemistry, National Dong Hwa University, Shoufeng Township, Hualien County 974, TaiwanThe total synthesis of (−)-antrocin and its enantiomer are presented. Antrocin (−)-<b>1</b> is an important natural product which acts as an antiproliferative agent in a metastatic breast cancer cell line (IC<sub>50</sub>: 0.6 <i>μ</i>M). The key features of this synthesis are: (a) selective anti-addition of trimethylsilyl cyanide (TMSCN) to <i>α,β</i>-unsaturated ketone; (b) resolution of (±)<b>-7</b> using chiral auxiliary L-dimethyl tartrate through formation of cyclic ketal diastereomers followed by simple column chromatography separation and acid hydrolysis; (c) substrate-controlled stereoselective aldol condensation of (+)-<b>12</b> with monomeric formaldehyde and pyridinium chlorochromate (PCC) oxidation for synthesis of essential lactone core in (−)-<b>14</b>; and (d) non-basic Lombardo olefination of the carbonyl at the final step to yield (−)-antrocin. In addition, (+)<b>-9</b> cyclic ketal diastereomer was converted to (+)-antrocin with similar reaction sequences.https://www.mdpi.com/1420-3049/25/4/831(−)-antrocindiastereoselective aldol reactionchiral resolutionnatural product synthesisnon-basic lombardo olefination |
| spellingShingle | Venkatachalam Angamuthu Dar-Fu Tai Synthesis of Natural (−)-Antrocin and Its Enantiomer via Stereoselective Aldol Reaction Molecules (−)-antrocin diastereoselective aldol reaction chiral resolution natural product synthesis non-basic lombardo olefination |
| title | Synthesis of Natural (−)-Antrocin and Its Enantiomer via Stereoselective Aldol Reaction |
| title_full | Synthesis of Natural (−)-Antrocin and Its Enantiomer via Stereoselective Aldol Reaction |
| title_fullStr | Synthesis of Natural (−)-Antrocin and Its Enantiomer via Stereoselective Aldol Reaction |
| title_full_unstemmed | Synthesis of Natural (−)-Antrocin and Its Enantiomer via Stereoselective Aldol Reaction |
| title_short | Synthesis of Natural (−)-Antrocin and Its Enantiomer via Stereoselective Aldol Reaction |
| title_sort | synthesis of natural antrocin and its enantiomer via stereoselective aldol reaction |
| topic | (−)-antrocin diastereoselective aldol reaction chiral resolution natural product synthesis non-basic lombardo olefination |
| url | https://www.mdpi.com/1420-3049/25/4/831 |
| work_keys_str_mv | AT venkatachalamangamuthu synthesisofnaturalantrocinanditsenantiomerviastereoselectivealdolreaction AT darfutai synthesisofnaturalantrocinanditsenantiomerviastereoselectivealdolreaction |