Asymmetric Synthesis of the Tricyclic Core of NGF-Inducing Cyathane Diterpenes via a Transition-Metal-Catalyzed [5 + 2] Cycloaddition

Abstract

[reaction: see text] A concise asymmetric synthesis of the tricyclic core of cyathane diterpenes is described, based on a novel transition-metal-catalyzed intramolecular [5 + 2] cycloaddition of ynone-vinylcyclopropane 10 (assembled from commercially available (S)-(-)-limonene), which proceeds in 90% yield with >95% selectivity. This strategy provides efficient access (14 steps and 13% overall yield) to potential analogues as well as precursors of nerve growth factor (NGF)-inducing diterpenes.