CHEMISTRY OF CAGE-SHAPED HYDROCARBONS - REACTIONS OF 6.0.0(2,6).0(3,13).0(10,14)]TETRADECANE-4,11-DIENE

A formal synthesis of peristylane 1 and oxaperistylane 3 are accomplis hed through chemical modifications of a cage-shaped molecule 6.0.0(2,6 ).0(3,13).0(10,14)]tetradecane-4,11-diene 2, Reaction of 2 with NBS re sulted in the formation of two dibromides 7 and 9 and a bromohydrin 8, Compound 9 was derived from 8 through bromination followed by a trans annular ring closure. Epoxidation of 2 with MCPBA produced an epoxide 15 and a diepoxide 13, both with the oxygen atoms oriented on the exo- side of the rings, Hydroboration of 2 followed by oxidation yielded a mixture of three isomeric diketones 20, 21 and 22, Oxaperistylane 3 wa s obtained from 21 by two successive reduction reactions. Peristylane 1 can be prepared from 22 by a known procedure, The structures of 9 an d 20 were characterized by single crystal X-ray diffraction analyses.