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Model Studies of β-Scission Ring-Opening Reactions of Cyclohexyloxy Radicals:  Application to Thermal Rearrangements of Dispiro-1,2,4-trioxanes

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journal contribution
posted on 20.12.2007, 00:00 by Stefan Erhardt, Stuart A. Macgregor, Kevin J. McCullough, Karen Savill, Benjamin J. Taylor
A DFT study of model cyclohexyloxy radicals (8ac, 9) show that (a) the presence of an adjacent oxygen atom, and (b) α-substituents on the cyclohexyl ring, particularly methoxy, accelerate the rate of β-scission ring-opening reactions. Consistent with theoretical results, thermolysis of the methoxy-substituted dispiro-1,2,4-trioxane 10 afforded the structurally novel, 14-membered macrocyclic keto lactone 11 as the major isolable product.