Heteroatom-directed Reverse Wacker Oxidations. Synthesis of the Reported Structure of (-)-Herbaric Acid

J Org Chem. 2010 Nov 5;75(21):7388-92. doi: 10.1021/jo1016585.

Abstract

A microwave-assisted chemoenzymatic resolution has been used to install the C3 stereocenter of the reported structure of the fungal metabolite herbaric acid in high enantiomeric excess. The synthesis and stereochemical assignment was accomplished using a completely regioselective anti-Markovnikov addition of water to vinylphthalide 3, achieved using a heteroatom-directed Wacker oxidation that proceeds with retention of stereochemistry. These results establish that so-called "reverse" Wacker oxidations are a viable alternative to hydroboration/oxidation procedures.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Biological Products / chemical synthesis*
  • Biological Products / chemistry*
  • Biological Products / metabolism
  • Fungi / metabolism
  • Heterocyclic Compounds, 2-Ring / chemical synthesis*
  • Heterocyclic Compounds, 2-Ring / chemistry*
  • Heterocyclic Compounds, 2-Ring / metabolism
  • Lactones / chemical synthesis*
  • Lactones / chemistry*
  • Lactones / metabolism
  • Oxidation-Reduction
  • Stereoisomerism
  • Substrate Specificity

Substances

  • Biological Products
  • Heterocyclic Compounds, 2-Ring
  • Lactones
  • herbaric acid