Umpolung Strategy for Synthesis of β-Ketonitriles through Hypervalent Iodine-Promoted Cyanation of Silyl Enol Ethers

J Org Chem. 2015 Jul 17;80(14):7212-8. doi: 10.1021/acs.joc.5b01102. Epub 2015 Jun 25.

Abstract

An efficient method to synthesize β-ketonitriles from silyl enol ethers by an umploung hypervalent iodine(III)-CN species generated in situ from PhIO/BF3·Et2O/TMSCN has been developed for the first time. This method can be applied to structurally diverse aromatic and aliphatic substrates and further extended to preparation of bioactive compounds like 5-aminopyrazole and 5-aminoisoxazole.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alcohols / chemistry*
  • Ethers / chemistry*
  • Iodine / chemistry*
  • Isoxazoles / chemical synthesis*
  • Isoxazoles / chemistry
  • Molecular Structure
  • Nitriles / chemical synthesis*
  • Nitriles / chemistry*
  • Pyrazoles / chemical synthesis*
  • Pyrazoles / chemistry
  • Stereoisomerism

Substances

  • 5-aminoisoxazole
  • 5-aminopyrazole
  • Alcohols
  • Ethers
  • Isoxazoles
  • Nitriles
  • Pyrazoles
  • Iodine