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NOTESAnal. Calcd for CllH1zOz: C, 74.98; H, 6.86. Found: C, 74.79; H, 6.91. 3-Bromo-3-phenyltetrahydro-2-pyrone (7).-Compound 6 (9.4 g, 0.0534 mole) in 25 ml of reagent grade CCld was added to 9.5

The synthesis of exo-7-isodeltacyclyl acetate was accomplished by conversion of the appropriate Diels-Alder adduct of ethyl trans-ß-acetoxyacrylate and cyclopentadiene to exo-o-acetoxy-endo-6-chlorocarbonylnorbornene, which was used to prepare exo-7-acetoxyisodeltacyclan-5-one, via intramolecular carbenoid addition brought about by Cu(II)-catalyzed decomposition of exo-5-acetoxy-endo-6-diazoacetylnorbornene. Reduction of the ethanedithiol ketal of exo-7-acetoxyisodeltacyclan-5-one with Raney nickel gave exo-7-isodeltacyclyl acetate.Acetolysis of exo-7-isodeltacyclyl brosylate generated exo-8-deltacyclyl acetate and exo-7-isodeltacyclyl acetate in a ratio of 96.3:3.7. Acetolysis of exo-7-isodeltacyclyl brosylate deuterated at C-5 produces exo-8-deltacyclyl acetate with deuterium distributed between C-9 and C-5 in a ratio of 1:1.8. These results are rationalized in terms of the direct generation of a norbornonium ion (13), which then leaks to the dissymmetric (C2) delocalized 8-deltacyclyl ion (3), with both intermediates producing product. The implications of these results as they bear on the solvolytic reactions of exo-and endo-8-deltacyclyl substrates are discussed.Our previous studies on the stereochemistry of the acetolyses of exo-and endo-8-deltacyclyl substrates (1 and 2), Pathways in the Base-Catalyzed Decomposition of Cyclic iV-Nitroso Carbamates1

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