A selenium-catalysed para-amination of phenols

Nat Commun. 2018 Oct 16;9(1):4293. doi: 10.1038/s41467-018-06763-4.

Abstract

Antioxidant enzyme glutathione peroxidase (GPx) decomposes hydroperoxides by utilizing the different redox chemistry of the selenium and sulfur. Here, we report a Se-catalysed para-amination of phenols while, in contrast, the reactions with sulfur donors are stoichiometric. A catalytic amount of phenylselenyl bromide smoothly converts N-aryloxyacetamides to N-acetyl p-aminophenols. When the para position was substituted (for example, with tyrosine), the dearomatization 4,4-disubstituted cyclodienone products were obtained. A combination of experimental and computational studies was conducted and suggested the weaker Se-N bond plays a key role in the completion of the catalytic cycle. Our method extends the selenium-catalysed processes to the functionalisation of aromatic compounds. Finally, we demonstrated the mild nature of the para-amination reaction by generating an AIEgen 2-(2'-hydroxyphenyl)benzothiazole (HBT) product in a fluorogenic fashion in a PBS buffer.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Amination
  • Benzothiazoles / chemistry
  • Catalysis
  • Nitrogen / chemistry
  • Phenols / chemistry*
  • Selenium / chemistry*
  • Selenium Compounds / chemistry
  • Sulfur / chemistry

Substances

  • Benzothiazoles
  • Phenols
  • Selenium Compounds
  • 2-(2-hydroxyphenyl)benzothiazole
  • Sulfur
  • Selenium
  • Nitrogen