Enantioselective Total Synthesis and Assignment of the Absolute Configuration of the Meroterpenoid (+)-Taondiol.

Abstract

The first enantioselective total synthesis of (+)-taondiol, a pentacyclic marine meroterpenoid, has been achieved, which in addition to confirming the structure also established the absolute configuration of the natural product. The notable points in the synthetic route are synthesis of a highly functionalized tricyclic diterpenoid moiety starting from an enantiopure Wieland-Miescher ketone derivative in concise manner via Robinson-type annulation and an elegant hydrogen atom transfer olefin reduction followed by Lewis acid-catalyzed Friedel-Crafts reaction for one-pot C-C and C-O bond formations resulting in construction of the pentacyclic meroterpenoid skeleton.