Stereoconvergent Negishi Arylations of Racemic Secondary Alkyl Electrophiles: Differentiating between a CF3 and an Alkyl Group

J Am Chem Soc. 2015 Aug 5;137(30):9523-6. doi: 10.1021/jacs.5b04725. Epub 2015 Jul 23.

Abstract

In this report, we establish that a readily available nickel/bis(oxazoline) catalyst accomplishes a wide array of enantioconvergent cross-couplings of arylzinc reagents with CF3-substituted racemic secondary alkyl halides, a process that necessitates that the chiral catalyst be able to effectively distinguish between a CF3 and an alkyl group in order to provide good ee. We further demonstrate that this method can be applied without modification to the catalytic asymmetric synthesis of other families of fluorinated organic compounds.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't

MeSH terms

  • Catalysis
  • Hydrocarbons, Brominated / chemistry*
  • Hydrocarbons, Fluorinated / chemical synthesis*
  • Hydrocarbons, Fluorinated / chemistry
  • Molecular Structure
  • Nickel / chemistry
  • Organometallic Compounds / chemistry
  • Oxazoles / chemistry
  • Stereoisomerism
  • Zinc / chemistry

Substances

  • Hydrocarbons, Brominated
  • Hydrocarbons, Fluorinated
  • Organometallic Compounds
  • Oxazoles
  • Nickel
  • Zinc