Triethylamine endoperoxides

Unusual triethylamine-catalysed rearrangements of bicyclic endoperoxides derived from substituted cycloheptatrienes have produced383 a variety of products (see, e.g., Scheme 80). Ab initio calculations have shown that energised 2,3-epoxypropoxide anions undergo a degenerate Payne rearrangement in the gas phase via a three-centre mechanism.384 It has been reported385 that treatment of isonitrile epoxides (330) with... 

Treatment of various cyclopropyl derivatives of the endoperoxide of 2,3-dioxabicyclo[2.2.2]oct-5-ene with triethylamine in dichloromethane resulted in an intramolecular redox reaction involving the peroxide moiety to give cyclopropyl hydroxyalkyl ketones. The yields were good dispiro[cyclopropane-l,5 -[2,3]dioxabicyclo[2.2.2]oct-7-ene-6, l"-cyclo-propane] (13) gave 10-hydroxydispiro[2.0.2.4]dec-8-en-7-one (14) in 80 /o yield. Treatment of similar unsaturated endoperoxides with alumina gave diketones, whereas thermolysis and photolysis of 13, like other unsaturated endoperoxides, afforded an mixture of an... 

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