A Family of New 1,2,4-Trioxanes by Photooxygenation of Allylic Alcohols in Sensitizer-Doped Polymers and Secondary Reactions

Abstract

Type II photooxygenation (singlet oxygen) is described as a synthetically useful way for the preparation of allylic hydro­peroxides and endoperoxides using sensitizer-adsorbed or covalently sensitizer-doped polymeric (macro- or nanosized) containers. Facilitated product separation and purification as well as increased reactivity are advantages of these techniques in comparison with solution-phase photochemistry. The products generated by Type II photooxygenation have been used for the syntheses of numerous polycyclic peroxides with a common 1,2,4-trioxane core as exhibited in the natural antimalarial artemisinin.

Key words

photochemistry - catalytic oxygenation - peroxides - peroxyacetals - Lewis acid catalysis

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1

X-ray structure analyses.

10

Griesbeck, A. G.; Bartoschek, A., unpublished results.

12

Griesbeck, A. G.;, Miara, C., unpublished results.

14

Griesbeck, A. G.; Höinck, L.-O., unpublished results.

28

Griesbeck, A. G.; El-Idreesy, T. T., unpublished results.