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A DFT study of model cyclohexyloxy radicals (8a−c, 9) show that (a) the presence of an adjacent oxygen atom, and (b) -substituents on the cyclohexyl ring, particularly methoxy, accelerate the rate of -scission ring-opening reactions. Consistent with theoretical results, thermolysis of the methoxy-substituted dispiro-1,2,4-trioxane 10afforded the structurally novel, 14-membered macrocyclic keto lactone 11as the major isolable product. [ABSTRACT FROM AUTHOR]