UBC Theses and Dissertations

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UBC Theses and Dissertations

Methylene addition to some 7-norbornadienyl derivatives Haywood-Farmer, John S.


The synthesis of exo-antl-tricyclo [3,2,1,02,4] octan-8-ol (V) and exo-anti-8-methoxy-tricyclo [3,2,1,02,4] octane (VI) was carried out by the cuprous chloride catalysed reaction of diazoraethane with anti-7-norbornenol (IV). The methyl ether (VI) was previously thought to be the endo isomer of (V). Methylene addition to the syn double bond of 7-norbornadienyl acetate (III) was accomplished using the above method to give a 5 to 1 mixture of exo-syn-tricyclo [3,2,1,02,4] oct-6-ene-8- acetate (VII) and endo-syn-tricyclo [3,2,1,02,4] oct-6-ene-8- acetate (VIII). These two acetates were inseparable but the corresponding alcohols exo-syn-tricyclo [3,2,1,02,4] oct-6-ene-8-ol (X) and endo-syn-tricyclo [3,2,1,02,4] oct-6-ene-8-ol (XI), formed by reduction of the acetate mixture with lithium aluminum hydride, could be separated by gas-liquid partition chromatography. The stereochemistry of these two products was determined by the multiplicity and by the chemical shift of the olefinic proton signals in their proton nuclear magnetic resonance spectra. Catalytic reduction of these two alcohols gave exo-syn-tricyclo [3,2,1,02,4] octan-8-ol (XIII) and endo-syn-trlcyclo [3,2,1,02,4] octan-8-ol (XIV). From the diazomethane-7-norbornadienyl acetate reaction a diadduct acetate, tetracyclo [3,3,1,02,4,06,8]nonan-9-acetate (IX), was also obtained which reduced to the alcohol tetracyclo [3,3,1,02,4,06,8] nonan-9-ol (XII). The stereochemistry of these diadducts was not determined. Acetolysis studies on the p-bromobenzene- sulfonyl (brosylate) derivative of exo-anti-tricyclo [3,2,1,02,4]octan-8-ol (V) at 200° indicate that the reaction proceeds by formation of a carbonium ion at C8, which then rearranges, destroying the cyclopropyl group. Although unchanged (V) could be obtained by lithium aluminum hydride reduction of about 80% solvolysed brosylate at 200°, none of the products of complete solvolysis could be identified.

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