1,2,5,10,11,14-Hexaoxadispiro[5.2.5.2]hexadecanes: Novel Spirofused Bis-Trioxane Peroxides

Molecules

Axel G. Griesbeck¹  Lars-Oliver Höinck¹  Johann Lex¹  Jörg Neudörfl¹  Dirk Blunk¹ 

[1] Department of Chemistry, Institute of Organic Chemistry, Greinstr. 4, 50939 Köln, Germany; E-mail:

关键词: Bis-spiro compounds;    peroxides;    singlet oxygen;    DFT calculations;    X-ray structure determination;   

DOI  :  10.3390/molecules13081743

来源: mdpi

【 摘 要 】

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.

【 授权许可】

CC BY   
© 2008 by the authors; licensee Molecular Diversity Preservation International, Basel, Switzerland.