The Formation of Bridged Bicyclic 1,2,4-Trioxanes by Intramolecular Capture of β-Hydroperoxy Cations

Article abstract of DOI:10.1002/hlca.19860690735

The 1,4-endoperoxide, prepared from 3-(4-methylnaphth-1-yl) propanal by photo-oxygenation in CH2Cl2, gave on treatment with Amberlyst-15, 3,10b-epidioxy-2,3,4a,10b-tetrahydro-6-methyl-1H-naphtho<2,1-b>pyran in 85percent yield.Its structure was determined by X-ray crystal structure analysis.The 1,2,4-trioxane moiety is locked in a twist-boat conformation with trans fusion to the parent six-membered ring.The 1,4-endoperoxides of the methyl, butyl, and phenyl ketone analogues of the aforementioned aldehyde underwent similar acid-catalyzed rearrangement to the corresponding bridged bicyclic trioxanes in 94,47, and 48percent yelds, respectively.