Synthetic Route Development for the Laboratory Preparation of Eupalinilide E

J Org Chem. 2017 May 5;82(9):4640-4653. doi: 10.1021/acs.joc.7b00266. Epub 2017 Apr 25.

Abstract

Following the discovery that the guaianolide natural product eupalinilide E promotes the expansion of hematopoietic stem and progenitor cells; the development of a synthetic route to provide laboratory access to the natural product became a priority. Exploration of multiple synthetic routes yielded an approach that has permitted a scalable synthesis of the natural product. Two routes that failed to access eupalinilide E were triaged either as a result of providing an incorrect diastereomer or due to lack of synthetic efficiency. The successful strategy relied on late-stage allylic oxidations at two separate positions of the molecule, which significantly increased the breadth of reactions that could be used to this point. Subsequent to C-H bond oxidation, adaptations of existing chemical transformations were required to permit chemoselective reduction and oxidation reactions. These transformations included a modified Luche reduction and a selective homoallylic alcohol epoxidation.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Laboratories
  • Oxidation-Reduction
  • Sesquiterpenes / chemical synthesis*

Substances

  • Sesquiterpenes
  • eupalinilide E