The mechanism of formation of 8,8-dimethyl[4.2.1.03,7]nonan-6-yl acetate (fortesyl acetate) during acetolysis of nopyl toluene-p-sulfonate

Abstract

Attempts to prepare 2-(2-hydroxyethyl)-6,6-dimethylbicyclo[3.1.1]hept-2-ene (nopol; 1) labelled with deuterium at C-10 by a process of oxidation of the primary alcohol group of nopol to the aldehyde, followed by H/D exchange and reduction back to alcohol, were unsuccessful because various oxidation procedures, including reaction with N-chlorosuccinimide at –78 °C, gave instead a carboxylic acid having an oxygen at C-3. Nopol, labelled at C-11 with deuterium, was obtained through a Prins reaction of β-pinene with deuteriated paraformaldehyde. This labelled nopol was converted into its toluene-p-sulfonate ester, and was solvolysed in acetic acid containing acetate ion to give 8,8-dimethyltricyclo[4.2.1.0^3,7]nonan-6-yl acetate, which is an earlier reported novel fused ring system (fortesyl acetate; 2 acetate). The position of the label in the product showed that the mechanism of this deep-seated carbon skeletal rearrangement proceeds through the intermediate formation of a cyclobutane ring, followed by shift of a methylene bridge to expand the original cyclobutane ring and then subsequent expansion of the new cyclobutane ring. Calculations of heats of formation of possible ions involved in these shifts confirm the proposed mechanism as the most likely pathway.