REARRANGEMENTS INVOLVING THE TRICYCLO[3.1.1.0(3,6)]HEPTYL AND TRICYCLO[3.2.1.0(3,6)]OCTYL SYSTEMS - SINGLE-ELECTRON TRANSFER IN THE REDUCTION OF A BRIDGEHEAD TOSYLATE WITH LITHIUM ALUMINUM-HYDRIDE

The attempted conversion of tricyclo[3.1.1.0(3,6)]heptane-6-methanol (9) into the corresponding tosylate (7) leads instead to a rearranged isomer tricyclo[3.2.1.0(3,6)]oct-6-yl tosylate (10). Treatment of (10) with lithium aluminium hydride affords a mixture of the parent alcohol tricyclo[3.2.1.0(3,6)]octan-6-ol (15) and endo-bicyclo[3.2.1]octan-6-ol. The available evidence suggests that the latter arises by a process which appears to be mediated by alkoxy radicals rather than anions.