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3-Azawurtzitane and 3(4 5)abeo-3-Azawurtzitane 3-Azawurtzitane (14) and 3(4 5)abeo-3-azawurtzitane (15) as well as derivatives thereof are described. The known tricyclic unsaturated ketone 1 was transformed to the properly functionalized endo-amines 3, 5 and 12. Entry to the azawurtzitane system and its corresponding abeo-compounds was achieved by three different cyclization procedures: aminomercuration with mercuric acetate in water (3 14, 5 16), olefin amination with mercuric acetate in dimethyl sulfoxide (3 18, 5 20 + 21) and intramolecular attack at an epoxide (12 24 + 25). Molecular rearrangements of 3-azawurtzitanes to 3(4 5)abeo-3-azawurtzitanes and vice versa are described involving neighbouring group participation of the N (3) atom.

A new synthesis of wurtzitane (13) is described starting from 2-oxo-protoadamant-4-ene (2). The key intermediate ketone 7 was obtained by regiospecific ring expansion of the β-amino alcohol 6. Entry to the wurtzitane system involved solvolysis of the tricyclic unsaturated mesylate 10 (11).