Aspects of Bicyclo (3,3,1) Nonane Chemistry

SECTION I: A study of the solvolytic behaviour of exo- and endo-1,5-dimethylbicyclo (3,3,1) nonan-9-one-2-yl tosylates revealed a stereochemical control in product formation which can best be explained in terms of ion-pair intermediates. Evidence for an acyl migration during solvolysis was found. SECTION II: A 2,6-hydride shift was discovered during the deuteration of exo-2-hydroxybicyclo (3,3,1) nonan-6-one. Studies of other possible 2,6-interactions in the bicyclo (3,3,1) skeleton, (i. e. homoenolisation between C2 and C6, synthesis of twistane derivatives from 2,6-disubstituted bicyclo (3,3,1) nonane compounds and reactivity of 6-hydroxy-2-cations) were also initiated. Finally the influence of a keto group at C6 and C9 on the solvolytic rate constant of the epimeric-2-tosylates was also studied and evidence found to support the current ideas regarding the influence of polar groups on ionisation of tosylates