Enantioselektive Synthese und Racemisierung von (−)‐Sinoracutin

A nearly‐30‐year‐old unanswered synthetic puzzle, astellatol, has been solved in an enantiospecific manner. The highly congested pentacyclic skeleton of this rare sesterterpenoid, which possesses a unique bicyclo[4.1.1]octane motif, ten stereocenters, a cyclobutane that contains two quaternary centers, an exo‐methylene group, and a sterically encumbered isopropyl trans‐hydrindane motif, makes astellatol arguably one of the most challenging targets for sesterterpenoid synthesis. An intramolecular Pauson–Khand reaction was exploited to construct the right‐hand side scaffold of this sesterterpenoid. An unprecedented reductive radical 1,6‐addition, mediated by SmI2, forged the cyclobutane motif. Last, a strategic oxidation/reduction step provided not only the decisive solution for the remarkably challenging late‐stage transformations, but also a highly valuable unravelling of the notorious issue of trans‐hydrindane synthesis. Importantly, the synthesis of astellatol showcases a rapid, scalable strategy to access diverse complex isopropyl trans‐hydrindane sesterterpenoids.

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Total Synthesis of Astellatol

Zhao

Yin

Xie

et al. 2018

Angewandte Chemie

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Limonin as a Starting Point for the Construction of Compounds with High Scaffold Diversity

2021

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Structurally complex natural products have been a fruitful source for the discovery and development of new drugs. In an effort to construct a compound collection populated by architecturally complex members with unique scaffolds, we have used the natural product limonin as a starting point. Limonin is an abundant triterpenoid natural product and, through alteration of its heptacyclic core ring system using short synthetic sequences, a collection of 98 compounds was created, including multiple members with novel ring systems. The reactions leveraged in the construction of these compounds include novel ring cleavage, rearrangements, and cyclizations, and this work is highlighted by the discovery of a novel B‐ring cleavage reaction, a unique B/C‐ring rearrangement, an atypical D‐ring cyclization, among others. Computational analysis shows that 52 different scaffolds/ring systems were produced during the course of this work, of which 36 are unprecedented. Phenotypic screening and structure–activity relationships identified compounds with activity against a panel of cancer cell lines.

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Asymmetric Total Synthesis of Hasubanan Alkaloids: Periglaucines A–C, N,O‐Dimethyloxostephine and Oxostephabenine

et al. 2022

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We report herein the asymmetric total synthesis of periglaucines A–C, N,O‐dimethyloxostephine and oxostephabenine. The key strategies used include: 1) a RhI‐catalyzed regio‐ and diastereoselective Hayashi‐Miyaura reaction to connect two necessary fragments; 2) an intramolecular photoenolization/Diels–Alder (PEDA) reaction to construct the highly functionalized tricyclic core skeleton bearing a quaternary center; 3) a bio‐inspired intramolecular Michael addition and transannular acetalization to generate the aza[4.4.3]propellane and the tetrahydrofuran ring.

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Enantioselektive Synthese und Racemisierung von (−)‐Sinoracutin

Cited by 8 publications

References 38 publications

Total Synthesis of Astellatol

Total Synthesis of Astellatol

Limonin as a Starting Point for the Construction of Compounds with High Scaffold Diversity

Asymmetric Total Synthesis of Hasubanan Alkaloids: Periglaucines A–C, N,O‐Dimethyloxostephine and Oxostephabenine

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