Spirofused and Annulated 1,2,4-Trioxepane-, 1,2,4-Trioxocane-, and 1,2,4-Trioxonane-Cyclohexadienones: Cyclic Peroxides with Unusual Ring Conformation Dynamics

Angelika Eske; Sabrina Ecker; Carolina Fendinger; Bernd Goldfuss; Matthis Jonen; Jens Lefarth; Jörg-M Neudörfl; Matthias Spilles; Axel G Griesbeck

doi:10.1002/anie.201807485

Spirofused and Annulated 1,2,4-Trioxepane-, 1,2,4-Trioxocane-, and 1,2,4-Trioxonane-Cyclohexadienones: Cyclic Peroxides with Unusual Ring Conformation Dynamics

Angew Chem Int Ed Engl. 2018 Oct 15;57(42):13770-13774. doi: 10.1002/anie.201807485. Epub 2018 Sep 17.

Authors

Angelika Eske¹, Sabrina Ecker¹, Carolina Fendinger¹, Bernd Goldfuss¹, Matthis Jonen¹, Jens Lefarth¹, Jörg-M Neudörfl¹, Matthias Spilles¹, Axel G Griesbeck¹

Affiliation

¹ Department of Chemistry, University of Cologne, Greinstr. 4, 50939, Köln, Germany.

PMID: 30091486
DOI: 10.1002/anie.201807485

Abstract

C3- or C4-hydroxyalkylated phenols are highly reactive towards peroxidation with oxone, which results in the formation of tertiary C3 hydroperoxides. This reaction can also be performed with photochemically generated singlet oxygen. However, other characteristic singlet oxygen reactions do not proceed with caroate. The initially formed hydroperoxides cyclize in the presence of a Lewis acid catalyst based on boron, indium, or iron to give spiroannulated peroxides. These exhibit restricted ring inversion whereas larger nine-membered-ring peroxides are thermally less stable and show higher ring flexibility (according to NMR analysis).

Keywords: heterocycles; oxygenation; peroxides; phenols; photochemistry.