SYNTHESE AB-TRANS-ANELLIERTER DERIVATE DES TRICYCLISCHEN DITERPENS PLEUROMUTILIN DURCH INTRAMOLEKULARE 1,5-HYDRID-VERSCHIEBUNG

Article abstract of DOI:10.1016/0040-4020(80)80078-0

The Diterpene Pleuromutilin(1) reacts with orthoformicacid-trimethylester at room temperature almost quantitatively to give the 11-keto-3-methylester 2 with AB-trans-configuration.This conversion is shown to occur through a 1,5-hydride-shift between C3 and C11.Treatment of 2 with Lewis acid (ZnCl2) initiated a retro-1,5-hydride-shift which resulted in the formation of Pleuromutilin(1).Mechanistic aspects and structure assignments, which are based on chemical and spectroscopic ((1)H- and (13)C-NMR) data are discussed.