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

Abstract

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.l]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.