Total Synthesis of (+)-Antrocin and Its Diastereomer and Clarification of the Absolute Stereochemistry of (−)-Antrocin

Huang, Sheng-Han; Liang, Kai-Hsiang; Lu, Jia‐Syun; Chang, Wen-Chih; Su, Ming‐Der; Yang, Te‐Fang

doi:10.1021/acs.joc.7b01600

Cited by 3 publications

(1 citation statement)

References 40 publications

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“…Another synthetic method for (+)-antrocin was reported [22] by Sheng-Han Huang et al Their tricyclic lactone core ring was constructed by an intramolecular Diels−Alder (IMDA) reaction of the camphanate-containing triene intermediate. However, this approach is associated with a long process which did not provide the required natural product (−)-1.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Natural (−)-Antrocin and Its Enantiomer via Stereoselective Aldol Reaction

Angamuthu

Tai

2020

Molecules

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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 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.

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Section: Introductionmentioning

confidence: 99%

Synthesis of Natural (−)-Antrocin and Its Enantiomer via Stereoselective Aldol Reaction

Angamuthu

Tai

2020

Molecules

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The Biosynthetic Gene Cluster of Mushroom‐Derived Antrocin Encodes Two Dual‐Functional Haloacid Dehalogenase‐like Terpene Cyclases

Chen

Lee

et al. 2023

Angewandte Chemie

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À )-Antrocin (1), produced by the medicinal mushroom Antrodia cinnamomea, is a potent antiproliferative compound. The biosynthetic gene cluster of 1 was identified, and the pathway was characterized by heterologous expression. We characterized a haloacid dehalogenase-like terpene cyclase AncC that biosynthesizes the drimane-type sesquiterpene (+)-albicanol (2) from farnesyl pyrophosphate (FPP). Biochemical characterization of AncC, including kinetic studies and mutagenesis, demonstrated the functions of two domains: a terpene cyclase (TC) and a pyrophosphatase (PPase). The TC domain first cyclizes FPP to albicanyl pyrophosphate, and the PPase domain then removes the pyrophosphate to form 2. Intriguingly, AncA (94 % sequence identity to AncC), in the same gene cluster, converts FPP into (R)-trans-γ-monocyclofarnesol instead of 2. Notably, Y283/F375 in the TC domain of AncA serve as a gatekeeper in controlling the formation of a cyclofarnesoid rather than a drimane-type scaffold.

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The Biosynthetic Gene Cluster of Mushroom‐Derived Antrocin Encodes Two Dual‐Functional Haloacid Dehalogenase‐like Terpene Cyclases

Chen

Lee

et al. 2023

Angew Chem Int Ed

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(−)‐Antrocin (1), produced by the medicinal mushroom Antrodia cinnamomea, is a potent antiproliferative compound. The biosynthetic gene cluster of 1 was identified, and the pathway was characterized by heterologous expression. We characterized a haloacid dehalogenase‐like terpene cyclase AncC that biosynthesizes the drimane‐type sesquiterpene (+)‐albicanol (2) from farnesyl pyrophosphate (FPP). Biochemical characterization of AncC, including kinetic studies and mutagenesis, demonstrated the functions of two domains: a terpene cyclase (TC) and a pyrophosphatase (PPase). The TC domain first cyclizes FPP to albicanyl pyrophosphate, and the PPase domain then removes the pyrophosphate to form 2. Intriguingly, AncA (94 % sequence identity to AncC), in the same gene cluster, converts FPP into (R)‐trans‐γ‐monocyclofarnesol instead of 2. Notably, Y283/F375 in the TC domain of AncA serve as a gatekeeper in controlling the formation of a cyclofarnesoid rather than a drimane‐type scaffold.

show abstract

Total Synthesis of (+)-Antrocin and Its Diastereomer and Clarification of the Absolute Stereochemistry of (−)-Antrocin

Cited by 3 publications

References 40 publications

Synthesis of Natural (−)-Antrocin and Its Enantiomer via Stereoselective Aldol Reaction

Synthesis of Natural (−)-Antrocin and Its Enantiomer via Stereoselective Aldol Reaction

The Biosynthetic Gene Cluster of Mushroom‐Derived Antrocin Encodes Two Dual‐Functional Haloacid Dehalogenase‐like Terpene Cyclases

The Biosynthetic Gene Cluster of Mushroom‐Derived Antrocin Encodes Two Dual‐Functional Haloacid Dehalogenase‐like Terpene Cyclases

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