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The Formation of Bridged Bicyclic 1,2,4‐Trioxanes by Intramolecular Capture of β‐Hydroperoxy Cations
Author(s) -
Jefford Charles W.,
Favarger France,
Ferro Serenella,
Chambaz Daniel,
Bringhen Alain,
Bernardinelli Gerald,
Boukouvalas John
Publication year - 1986
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19860690735
Subject(s) - chemistry , bicyclic molecule , moiety , intramolecular force , ketone , aldehyde , ring (chemistry) , pyran , stereochemistry , yield (engineering) , trioxane , acetal , medicinal chemistry , catalysis , organic chemistry , materials science , polymer , copolymer , metallurgy
The 1,4‐endoperoxide, prepared from 3‐(4‐methylnaphth‐1‐yl)propanal by photo‐oxygenation in CH 2 Cl 2 , gave on treatment with Amberlyst ‐ 15 ®, 3,10b‐epidioxy‐2,3,4a,10b‐tetrahydro‐6‐methyl‐1 H ‐naphtho[2,1‐ b ] pyran in 85% 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 48% yields, respectively.