Total synthesis of gambierol: the generation of the A-C and F-H subunits by using a C-glycoside centered strategy

Chemistry. 2006 Feb 8;12(6):1736-46. doi: 10.1002/chem.200500993.

Abstract

Gambierol, a representative of the marine ladder toxin family, consists of eight ether rings, 18 stereocenters, and two challenging pyranyl rings having methyl groups that are in a 1,3-diaxial orientation to one another. Herein we describe the generation of gambierol's A-C and F-H ring systems and demonstrate the versatility of the glycosyl anhydride, enol ether-olefin RCM strategy to fused polycyclic ethers. This work has both enabled us to generate sufficient quantities of the gambierol precursors and has enabled us to better understand the chemical transformations that were key to these efforts. Fundamental work included efforts to C-glycosides and C-ketosides, Claisen rearrangements, and enol ether-olefin RCM reactions.

Publication types

  • Research Support, N.I.H., Extramural

MeSH terms

  • Ciguatera Poisoning
  • Ciguatoxins / chemical synthesis*
  • Cyclization
  • Epoxy Compounds / chemical synthesis
  • Ethers / chemistry
  • Ethers, Cyclic / chemical synthesis*
  • Glycosides / chemical synthesis*
  • Indicators and Reagents
  • Magnetic Resonance Spectroscopy
  • Marine Toxins / chemical synthesis*
  • Polycyclic Compounds / chemical synthesis*
  • Polycyclic Compounds / chemistry

Substances

  • Epoxy Compounds
  • Ethers
  • Ethers, Cyclic
  • Glycosides
  • Indicators and Reagents
  • Marine Toxins
  • Polycyclic Compounds
  • gambierol
  • Ciguatoxins