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Synthesis of Natural (-)-Antrocin and its Enantiomer via Stereoselective Aldol Reaction.

ABSTRACT: The total synthesis of (-)-antrocin and its enantiomer are presented. Antrocin (-)-1 is an important natural product which acts as an antiproliferative agent in a metastatic breast cancer cell line (IC50: 0.6 ?M). The key features of this synthesis are: (a) selective anti-addition of trimethylsilyl cyanide (TMSCN) to ?,?-unsaturated ketone; (b) resolution of (±)-7 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 (+)-12 with monomeric formaldehyde and pyridinium chlorochromate (PCC) oxidation for synthesis of essential lactone core in (-)-14; and (d) non-basic Lombardo olefination of the carbonyl at the final step to yield (-)-antrocin. In addition, (+)-9 cyclic ketal diastereomer was converted to (+)-antrocin with similar reaction sequences.

SUBMITTER: Angamuthu V

PROVIDER: S-EPMC7070359 | biostudies-literature | 2020 Feb

REPOSITORIES: biostudies-literature

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Synthesis of Natural (-)-Antrocin and its Enantiomer via Stereoselective Aldol Reaction.

Angamuthu Venkatachalam V Tai Dar-Fu DF

Molecules (Basel, Switzerland) 20200214 4

The total synthesis of (-)-antrocin and its enantiomer are presented. Antrocin (-)-1 is an important natural product which acts as an antiproliferative agent in a metastatic breast cancer cell line (IC50: 0.6 μM). The key features of this synthesis are: (a) selective anti-addition of trimethylsilyl cyanide (TMSCN) to α,β-unsaturated ketone; (b) resolution of (±)-7 using chiral auxiliary L-dimethyl tartrate through formation of cyclic ketal diastereom ...[more]

PMID: 32075004

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