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Issue 44, 2017
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Total syntheses of all tri-oxygenated 16-phytoprostane classes via a common precursor constructed by oxidative cyclization and alkyl–alkyl coupling reactions as the key steps

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Abstract

A unified strategy for the total synthesis of the methyl esters of all phytoprostane (PhytoP) classes bearing two ring-oxygen atoms based on an orthogonally protected common precursor is described. Racemic 16-F1t-, 16-E1-PhytoP and their C-16 epimers, which also occur as racemates in Nature, were successfully obtained. The first total synthesis of very sensitive 16-D1t-PhytoP succeeded, however, it quickly isomerized to more stable, but so far also unknown Δ13-16-D1t-PhytoP, which may serve as a more reliable biomarker for D-type PhytoP. The dioxygenated cyclopentane ring carrying the ω-chain with the oxygen functionality in the 16-position was approached by a radical oxidative cyclization mediated by ferrocenium hexafluorophosphate and TEMPO. The α-chain was introduced by a new copper-catalyzed alkyl–alkyl coupling of a 6-heptenyl Grignard reagent with a functionalized cyclopentylmethyl triflate.

Graphical abstract: Total syntheses of all tri-oxygenated 16-phytoprostane classes via a common precursor constructed by oxidative cyclization and alkyl–alkyl coupling reactions as the key steps

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Publication details

The article was received on 10 Oct 2017, accepted on 24 Oct 2017 and first published on 24 Oct 2017


Article type: Paper
DOI: 10.1039/C7OB02505J
Citation: Org. Biomol. Chem., 2017,15, 9408-9414
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    Total syntheses of all tri-oxygenated 16-phytoprostane classes via a common precursor constructed by oxidative cyclization and alkyl–alkyl coupling reactions as the key steps

    J. Smrček, R. Pohl and U. Jahn, Org. Biomol. Chem., 2017, 15, 9408
    DOI: 10.1039/C7OB02505J

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