• Hydrative Aminoxylation of Ynamides: One Reaction, Two Mechanisms

    • Alexandre Pinto
      Department of Organic Chemistry, Faculty of Chemistry, University of Vienna
    • Daniel Kaiser
      Department of Organic Chemistry, Faculty of Chemistry, University of Vienna
    • Boris Maryasin
      Department of Organic Chemistry, Faculty of Chemistry, University of Vienna
    • Giovanni Di Mauro
      Department of Organic Chemistry, Faculty of Chemistry, University of Vienna
    • Leticia González
      Department of Theoretical Chemistry, Faculty of Chemistry, University of Vienna
    • Nuno Maulide
      Department of Organic Chemistry, Faculty of Chemistry, University of Vienna
  • Organic synthesis boasts a wide array of reactions involving either radical species or ionic intermediates. The combination of radical and polar species, however, has not been explored to a comparable extent. Herein we present the hydrative aminoxylation of ynamides, a reaction which can proceed by either a polar‐radical crossover mechanism or through a rare cationic activation. Common to both processes is the versatility of the persistent radical TEMPO and its oxidised oxoammonium derivative TEMPO+. The unique mechanisms of these processes are elucidated experimentally and by in‐depth DFT‐calculations.

  • PDF

  • http://phaidra.univie.ac.at/o:1005830

  • Article

  • Published Version

  • 2018

  • 24

  • 10

  • 2515-2519

  • Wiley

  • English

  • Open access

  • CC BY Attribution 4.0 International
    © 2018 The Authors

  • 30226 – Austrian Science Fund (FWF)

  • 482002 – European Union (all programmes)

  • DOC – Österreichische Akademie der Wissenschaften (ÖAW)

  • 0947-6539

  • aminoxylation; density functional calculations; heterocycles; radicals; reaction mechanisms