engleski

Synthesis and chemistry of sesqui-icyclo[2.2.2]octene and a tetradecacyclic-caged sesquibicyclo[2.2.2]octene

Cationic rearrangements of functionalized spiro(norbornane-7, 3'-bicyclo[2.2.2]octan-2'-ols) provide synthetic access to two novel polycarbocyclic alkenes, i.e., 5 and 10 (''sesquibicyclo[2.2.2]octene''). X-ray crystallographic analysis of 5 and 10 reveals that each alkene C=C double bond is planar in the crystalline solid. MCPBA promoted epoxidation of 5 produced the corresponding oxirane, 11. Ring opening of the highly labile oxirane moiety in 11 occurred in the presence of mild Lewis acids (e.g., silica gel) or bases (e.g., NaHCO3), thereby affording the corresponding cis-diol, 12. MCPBA promoted epoxidation of 7 afforded the corresponding oxirane, 13. Oxirane 13 proved to be considerably less labile than 11 toward acidic and/or basic media.

cage compounds; promoted reductive dimerization; pinacols

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