Rearrangements Involving the Tricyclo[3.1.1.03,6]heptyl and Tricyclo[3.2.1.03,6]octyl Systems. Single-Electron Transfer in the Reduction of a Bridgehead Tosylate With Lithium Aluminum Hydride

Abstract

The attempted conversion of tricyclo [3.1.1.03,6]heptane-6-methanol (9) into the corresponding tosylate (7) leads instead to a rearranged isomer tricyclo [3.2.1.03,6]oct-6-yl tosylate (10). Treatment of 10 with lithium aluminium hydride affords a mixture of the parent alcohol tricyclo[3.2.1.03,6]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.

Correlation of Gas-Phase Stability of Bridgehead Carbocations with Rates of Solvolysis and ab Initio Calculations

“…1-Bromobicyclo[2.2.2]octane ( 4 ) was synthesized according to the procedure of Morita et al . Bromocubane ( 6 ), 6-bromotricyclo[3.2.1.0 3,6 ]octane ( 10 ), homocubane-4-carboxylic acid, and 1-bromohomocubane ( 8 ) were prepared as described .…”

The formation of bicyclo[n.2.0]alkan-1-ols from the reaction of the lithium enolates of simple ketones and phenyl vinyl sulfoxideElectronic supplementary information (ESI) available: full experimental details. See http://www.rsc.org/suppdata/ob/b2/b208365e/

“…See http://www.rsc.org/suppdata/ob/b2/b208365e/ photocycloaddition of bicyclo [3.3.1]nonanediones to allene, 7 photochemical cyclisation of aliphatic 4-oxoacetals, 8 cycloaddition of a silylenol ether with propynoates, 9 arynic condensation of ketone enolates, 10 condensation of dehydro dihydropyrans with ketone enolates, 11 and Norrish type-II cyclization. 12 Rearrangements are also observed and include rearrangement of tricyclo[3.1.1.0 3,6 ]heptyl and tricyclo[3.2.1.0 3,6 ]octyl systems, 13 cationic rearrangement of α-aryl pentacyclooctanes, 14 and solvolysis of substituted cyclopropyl carbinylic systems to include ring enlargement to form substituted cyclobutanols. 15 Other transformations include Clemmensen reduction of strained diketones, 16 intramolecular reductive ring closure with samarium iodide of alkene chloroketones, 17 samarium diiodidemediated pinacolization of diketones, 18 and reduction of α-acetoxy ketones.…”