Irreversible endo-selective diels-alder reactions of substituted alkoxyfurans: a general synthesis of endo-cantharimides

Chemistry. 2015 Apr 13;21(16):6107-14. doi: 10.1002/chem.201406286. Epub 2015 Mar 10.

Abstract

The [4+2] cycloaddition of 3-alkoxyfurans with N-substituted maleimides provides the first general route for preparing endo-cantharimides. Unlike the corresponding reaction with 3H furans, the reaction can tolerate a broad range of 2-substitued furans including alkyl, aromatic, and heteroaromatic groups. The cycloaddition products were converted into a range of cantharimide products with promising lead-like properties for medicinal chemistry programs. Furthermore, the electron-rich furans are shown to react with a variety of alternative dienophiles to generate 7-oxabicyclo[2.2.1]heptane derivatives under mild conditions. DFT calculations have been performed to rationalize the activation effect of the 3-alkoxy group on a furan Diels-Alder reaction.

Keywords: cantharimides; cycloadditions; dienes; furans; phthalimide.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alcohols / chemical synthesis
  • Alcohols / chemistry*
  • Bridged Bicyclo Compounds, Heterocyclic / chemical synthesis*
  • Cycloaddition Reaction / methods*
  • Furans / chemical synthesis
  • Furans / chemistry*
  • Maleimides / chemical synthesis
  • Maleimides / chemistry
  • Models, Molecular

Substances

  • 7-oxabicyclo(2.2.1)heptane
  • Alcohols
  • Bridged Bicyclo Compounds, Heterocyclic
  • Furans
  • Maleimides
  • alkoxyl radical