Photoredox-Catalyzed Radical Cyclization of Unactivated Alkene-Substituted β-Ketoesters Enabled Asymmetric Total Synthesis of Tricyclic Prostaglandin D(2) Metabolite Methyl Ester

光氧化还原催化未活化烯烃取代β-酮酯的自由基环化反应实现了三环前列腺素D(2)代谢物甲酯的不对称全合成

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Abstract

Regio- and stereoselective photoredox-catalyzed cyclizations of alkene-substituted β-ketoesters have been accomplished for the synthesis of polyfunctionalized cyclopentanones. This was achieved using 2,3,5,6-tetrakis(carbazol-9-yl)-1,4-dicyanobenzene (4CzTPN) and 2,4,6-triisopropyl-thiophenol as cocatalysts under illumination of a blue-light-emitting-diode at ambient temperature. The developed chemistry was successfully applied in the enantioselective total synthesis of the tricyclic prostaglandin D(2) metabolite (tricyclic-PGDM) methyl ester, which was completed in 9 steps with an overall yield of 7%.

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