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Stereocontrolled access to isoprostanes via a bicyclo[3.3.0]octene framework
Camille Oger1, Yasmin Brinkmann, Samira Bouazzaoui
1Institut des Biomolécules Max Mousseron, IBMM, UMR CNRS 5247, Université Montpellier I, Faculté de Pharmacie, 15. Av. Ch. Flahault, F-34093 Montpellier cedex 05, France.
Abstract:
We report a simple and highly stereocontrolled strategy toward the total synthesis of isoprostanes based on a bicyclic alpha,beta-epoxy ketone intermediate 6. Bicyclo[3.3.0]octene scaffold permitted stereodirection of reagents allowing stereoselective epoxidation, diastereoselective ketone reduction, and regioselective epoxide opening otherwise not accessible with a simple cyclopentene framework.
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Preparation of Epoxides
Epoxides result from alkene oxidation, which can be achieved by a) air, b) peroxy acids, c) hypochlorous acids, and d) halohydrin cyclization.
Epoxidation with Peroxy Acids
Epoxidation of alkenes via oxidation with peroxy acids involves the conversion of a carbon–carbon double bond to an epoxide using the oxidizing agent meta-chloroperoxybenzoic acid, commonly known as MCPBA. Since the O–O bond of peroxy acids is very weak, the addition of electrophilic oxygen of peroxy acids to...

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