Issue 44, 2017

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

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

Supplementary files

Article information

Article type
Paper
Submitted
10 Oct 2017
Accepted
24 Oct 2017
First published
24 Oct 2017
This article is Open Access
Creative Commons BY-NC license

Org. Biomol. Chem., 2017,15, 9408-9414

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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