Polar-to-Radical Crossover in Catalyst-Free Olefin Halo-Hydroxylamination: A Direct Route to Multifunctional Electrophilic Hydroxylamines

Herein, we introduce a powerful alkene difunctionalization process where anomeric amides (i.e., N-halogenated-O-activated hydroxylamines) react directly with olefins, without the use of catalysts or additives, to yield the corresponding N-haloalkyl-O-activated hydroxylamines. These multifunctional hydroxylamines (MFHAs), containing both alkyl halide and O-activated hydroxylamine moieties, are convenient building blocks/electrophilic aminating reagents for the synthesis of structurally complex N-unprotected secondary amines and various N-heterocycles (i.e., N-alkyl/N-aryl aziridines, pyrrolidines, oxazolidinones and tetrahydroquinolines). Both activated and unactivated alkenes (including cyclic and acyclic…

• WF
  Welch Foundation

  Awards: C-2247, C-1764
• BY
  Brigham Young University
• RU
  Rice University
• NI
  National Institute of General Medical Sciences

  Awards: R35 GM136370, R35 GM-136373
• DO
  Division of Chemistry

  Award: CHE-2244799