3-Bicyclo octyl brosylates

When bicyclo[2.2.2]octyl brosylate was solvolyzed in acetic acid containing sodium acetate, the products were a mixture of bicyclo[2.2.2]octyl acetate and bicyclo[3.2.1]octyl acetate, each of which was optically active. The formation of bicyclo[2.2.2]octyl acetate was found to proceed with 82 15% retention of configuration, a result which is in... 

Cope and coworkers carried out a product study on acetolysis of the epimeric 3-bicyclo[5.1.0]octyl brosylates (135 and 136) (Scheme 19). However, no kinetics were measured. Formation of the bicyclo[3.3.1]octan-3-yl product from the endo brosylate (135) reveals that some cyclopropyl participation may be involved. 

SCHEME 19 Products of acetolysis of epimeric 3-bicyclo[5.1.0]octyl brosylates ... 

When bicyclo[2.2.2]octyl brosylate was solvolyzed in acetic acid containing sodium acetate, the products were a mixture of bicyclo[2.2.2]octyl acetate and... 

Bicyclooctyl Cations. Solvolyses of endo-2-bicyclo[3.2.1]octyl tosylate (73)55S and 4-cycloheptenylcarbinyl brosylate (4< 7)377 555 give similar product mixtures consisting primarily of endo-2-bicyclo [3.2.1] octanol or its acetate (819)... 

The acetolysis of optically active brosylate 157 results in an optically active bicyclo[2,2,2]acetate 160 with 85 15% retention of configuration the second product — the axial 2-bicyclo[3,2,l]octyl acetate 161 (63 35) — turned out to be optically active as well. Not even any traces were found of the more stable equatorial isomer 162. From these data the authors concluded an intervention of the nonclassical ion 158. The degree of retention (85 15%), however, does not preclude the classical ion 159 to play a minor role as well. 

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