1,2,5,10,11,14-hexaoxadispiro[5.2.5.2]hexadecanes: novel spirofused bis-trioxane peroxides.
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 BF(3)-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.
Griesbeck
Axel G
AG
Department of Chemistry, Institute of Organic Chemistry, Greinstr. 4, 50939 Köln, Germany. griesbeck@uni-koeln.de
Höinck
Lars-Oliver
LO
Lex
Johann
J
Neudörfl
Jörg
J
Blunk
Dirk
D
El-Idreesy
Tamer T
TT
D003510:Cyclohexanes / Q000737:chemistry; D006571:Heterocyclic Compounds / Q000138:chemical synthesis / Q000737:chemistry; D006861:Hydrogen Peroxide / Q000737:chemistry; D015394:Molecular Structure; D010545:Peroxides / Q000138:chemical synthesis* / Q000737:chemistry; D013141:Spiro Compounds / Q000138:chemical synthesis* / Q000737:chemistry
D003510:Cyclohexanes; D006571:Heterocyclic Compounds; D010545:Peroxides; D013141:Spiro Compounds; C506365:Cyclohexane; D006861:Hydrogen Peroxide
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