Abstract: A set of new bis-spirofused 1,2,4-trioxanes 4a-d was obtained from the reaction of cyclohexane-1,4-dione with allylic hydroperoxides 2a-d, bearing an additional hydroxy group in the homoallylic position, by diastereoselective photooxygenation of allylic alcohols 1a-d and subsequent BF3-catalyzed peroxyacetalization with the diketone. From the reaction of a monoprotected cyclohexane-1,4-dione 5 with the allylic hydroperoxide 6 derived from the singlet oxygenation of methyl hydroxytiglate, one monospiro compound was obtained, the 1,2,4-trioxane ketone 7, as well as a mixture of the diastereoisomeric syn- and anti bis-1,2,4-trioxanes 8. The structures of bis-1,2,4-trioxanes were examined theoretically by DFT methods and compared with X-ray structural data in order to evaluate the preferential trioxane ring conformational orientation.
Keywords: Bis-spiro compounds; peroxides; singlet oxygen; DFT calculations; X-ray structure determination.
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Griesbeck, A.G.; Höinck, L.-O.; Lex, J.; Neudörfl, J.; Blunk, D.; El-Idreesy, T.T. 1,2,5,10,11,14-Hexaoxadispiro[188.8.131.52]hexadecanes: Novel Spirofused Bis-Trioxane Peroxides. Molecules 2008, 13, 1743-1758.
Griesbeck AG, Höinck L-O, Lex J, Neudörfl J, Blunk D, El-Idreesy TT. 1,2,5,10,11,14-Hexaoxadispiro[184.108.40.206]hexadecanes: Novel Spirofused Bis-Trioxane Peroxides. Molecules. 2008; 13(8):1743-1758.
Griesbeck, Axel G.; Höinck, Lars-Oliver; Lex, Johann; Neudörfl, Jörg; Blunk, Dirk; El-Idreesy, Tamer T. 2008. "1,2,5,10,11,14-Hexaoxadispiro[220.127.116.11]hexadecanes: Novel Spirofused Bis-Trioxane Peroxides." Molecules 13, no. 8: 1743-1758.