Synthesis of the C13-C29 fragment of leiodolide A: Allylic asymmetric induction on the stereochemical course of iodolactonization

Abstract

A stereocontrolled synthesis of the C13-C29 segment of leiodolide A is described. This natural product was isolated from the deep-water marine sponge Leiodermatium. A highly selective Stille cross-coupling was employed to assemble the (Z,E)-diene bearing the C15 allylic alcohol, which was followed by iodolactonization to introduce C16-C17 vicinal stereocenters. The stereochemical course of iodolactonization that is based on the solid mechanistic underpinnings arising from allylic asymmetric induction is also discussed. © 2015 Elsevier Ltd. All rights reserved.