13C magnetic resonance studies. 138. An examination of the [3.2.2.0] → [4.2.1.0] rearrangement via β-enolization and H/D exchange in tricyclic ketones

Abstract

The behavior of the endo and exo isomers of 7,7-dimethyltricyclo[3.2.2.02,4]nonan-6-one (9, 17) under strongly basic conditions (t-BuO−/t-BuOH/185 °C) has been examined. In both cases rearrangement to the corresponding 8,8-dimethyl-tricyclo[4.2.1.02,4]nonan-7-one (11, 18) was found, with the exo isomer reacting approximately 8 times faster. Experiments in tert-butyl alcohol-O-d1 were carried out to determine the specific sites, the relative rates, and the stereochemistry of deuterium incorporation in the initial ketones. Although H/D exchange occurs most readily at the cyclopropyl methylene carbon in the endo isomer, none of the rearrangement product expected to arise via γ-enolate formation was observed. The results for these ketones are compared with our earlier observations in the related [2.2.2], [3.2.1.0], and [3.3.1.0] systems. Keywords: homoenolization, tricyclic ketones, H/D exchange.