Unifying the Synthesis of a Whole Family of Marine Meroterpenoids through a Biosynthetically Inspired Sequence of 1,2-Hydride and Methyl Shifts as Key Step

Abstract

Marine meroterpenoids have attracted a great deal of attention from synthetic research groups due to their attractive and varied biological activities and their unique and diverse structures. In most cases, however, further biological studies have been severely limited mainly to the scarcity of natural supply and because almost none of the reported syntheses methods has enabled unified access for a large number of marine meroterpenoids with aureane and avarane skeletons. Based on our previous publications and the study of recent manuscripts on marine meroterpenoids, we have conceived a unified strategy for these fascinating marine compounds with aureane or avarane skeletons using available drimane compounds as starting materials. The key step is a biosynthetic sequence of 1,2-hydride and methyl shifts. This strategy is of great synthetic value to access marine meroterpenoids through easy chemical synthetic procedures. Finally, several retrosynthetic proposals are made for the future synthesis of several members of this class of meroterpenoids, focused on consolidating these 1,2-rearrangements as a versatile and unified strategy that could be widely used in the preparation of these marine meroterpenoids.

Keywords

• marine natural products
• meroterpenoids
• rearrangements
• synthetic strategies