Asymmetric Total Synthesis of (-)-Spirochensilide A, Part 1: Diastereoselective Synthesis of the ABCD Ring and Stereoselective Total Synthesis of 13(R)-Demethyl Spirochensilide A

J Org Chem. 2021 Feb 5;86(3):2135-2157. doi: 10.1021/acs.joc.0c02494. Epub 2021 Jan 12.

Abstract

A concise and diastereoselective construction of the ABCD ring system of spirochensilide A is described. The key steps of this synthesis are a semipinacol rearrangement reaction to stereoselectively construct the AB ring system bearing two vicinal quaternary chiral centers and a Co-mediated Pauson-Khand reaction to form the spiro-based bicyclic CD ring system. This chemistry leads to the stereoselective synthesis of 13(R)-demethyl spirochensilide A, paving the way for the first asymmetric total synthesis of (-)-spirochensilide A.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Stereoisomerism
  • Triterpenes*

Substances

  • Triterpenes
  • spirochensilide A