Oxidative Dearomatization of 4,5,6,7-Tetrahydro-1H-indoles Obtained by Metal- and Solvent-Free Thermal 5-endo-dig Cyclization: The Route to Erythrina and Lycorine Alkaloids

Chemistry. 2016 May 17;22(21):7262-7. doi: 10.1002/chem.201600273. Epub 2016 Apr 14.

Abstract

A facile one-pot approach based on a thermally induced metal- and solvent-free 5-endo-dig cyclization reaction of the amino propargylic alcohols in combination with Dess-Martin periodinane-promoted oxidative dearomatization of 4,5,6,7-tetrahydroindole intermediates provides an efficient and robust access to 5,6-dihydro-1H-indol-2(4H)ones. Green, relatively mild and operationally simple characteristics of the synthetic sequence are the major advantages, which greatly amplify the developed methodology. The utility of obtained indolones as unified key precursors is demonstrated by the application of these products to the formal total syntheses of a whole pleiad of Erythrina- and Lycorine-type alkaloids, namely (±)-erysotramidine, (±)-erysotrine, (±)-erythravine, (±)-γ-lycorane, and abnormal erythrinanes (±)-coccoline and (±)-coccuvinine.

Keywords: 4,5,6,7-tetrahydroindoles; alkaloids; green chemistry; thermally induced cyclization; total synthesis.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alkaloids / chemical synthesis*
  • Alkaloids / chemistry
  • Amaryllidaceae Alkaloids / chemical synthesis*
  • Amaryllidaceae Alkaloids / chemistry
  • Cyclization
  • Erythrina / chemistry*
  • Green Chemistry Technology / methods
  • Hydrocarbons, Iodinated / chemical synthesis
  • Hydrocarbons, Iodinated / chemistry
  • Indoles / chemical synthesis
  • Indoles / chemistry*
  • Oxidation-Reduction
  • Phenanthridines / chemical synthesis*
  • Phenanthridines / chemistry
  • Stereoisomerism
  • Temperature

Substances

  • Alkaloids
  • Amaryllidaceae Alkaloids
  • Hydrocarbons, Iodinated
  • Indoles
  • Phenanthridines
  • 1,1,1-triacetoxy-1,1-dihydro-1,2-benziodoxol-3(1H)-one
  • lycorine