Tandem Alkyne Hydroacylation and Oxo-Michael Addition: Diastereoselective Synthesis of 2,3-Disubstituted Chroman-4-ones and Fluorinated Derivatives

Org Lett. 2015 Jul 2;17(13):3276-9. doi: 10.1021/acs.orglett.5b01447. Epub 2015 Jun 22.

Abstract

Tandem reactions involving Rh-catalyzed intermolecular hydroacylations of alkynes with salicylaldehydes followed by intramolecular oxo-Michael additions are described for the diastereoselective synthesis of 2,3-disubstituted chroman-4-ones. The tandem hydroacylation/oxo-Michael additions occur to form 2,3-disubstituted chroman-4-ones in high yields from a range of 1,2-disubstituted acetylenes and substituted salicylaldehyes. The resulting 2,3-disubstituted chroman-4-ones are readily fluorinated to form trans-3-fluoro-2,3-disubstituted chroman-4-ones in high yields with excellent diastereoselectivity.

Publication types

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

MeSH terms

  • Aldehydes / chemistry
  • Alkynes / chemistry*
  • Catalysis
  • Chromones / chemical synthesis*
  • Chromones / chemistry
  • Halogenation
  • Hydrocarbons, Fluorinated / chemical synthesis*
  • Hydrocarbons, Fluorinated / chemistry
  • Molecular Structure
  • Rhodium / chemistry*
  • Stereoisomerism

Substances

  • Aldehydes
  • Alkynes
  • Chromones
  • Hydrocarbons, Fluorinated
  • salicylaldehyde
  • Rhodium