Diastereoselective SmI2 mediated cascade radical cyclisations of methylenecyclopropane derivatives—syntheses of paeonilactone B and 6-epi-paeonilactone A

Abstract

The SmI₂ mediated cascade cyclisations of several methylenecyclopropyl ketones have been examined and found to proceed with high diastereoselectivity, which is critically dependent on the presence of HMPA in the reaction. In one case the radical species at the end of the cascade sequence underwent an unexpected and highly stereoselective dimerisation. The cascade methodology has been applied to a short synthesis of (±)-paeonilactone B and of (±)-6-epi-paeonilactone A.