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An intramolecular, base-catalyzed ring closure of ezo-bicyclo[3.2.1 ]octan-6-on-3-yl tosylate (6) furnished the symmetrical ketone, tricyclo[3.2.1.03 45•6]octan-7-one (4), in good yield. The bicyclic precursor 6 was prepared from dehydronorcamphor by the sequence: dichlorocarbene addition and ring expansion, reductive removal of the two chlorine atoms, and introduction of the exo-C3 oxygen atom by hydroboration-oxidation. The stereoselective and regioselective nature of the hydroboration reaction was established unambiguously. Wolff-Kishner reduction of ketone 4 gave the known parent hydrocarbon. Baeyer-Villiger oxidation of 4 gave a single lactone resulting from formal migration of the cyclobutane ring. Product distribution and deuterium label scrambling results suggest that solvolysis of tricyclo[3.2.1.03•6]octan-7-yl tosylate proceeds through a symmetrical, degenerate tricyclic cation to yield both tricyclic and bicyclic products.

Das 1,4‐ Cyclohexadien (I) liefert über eine in‐situ‐Isomerisierung zu (II) mit α‐Chloracrylnitril (III) die isomeren Addukte (IV), die zum Keton (Va) hydrolysiert werden.

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