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Hypoiodite-Catalyzed Oxidative Umpolung of Indoles for Enantioselective Dearomatization.

Hiroki TanakaNaoya UkegawaMuhammet UyanikKazuaki Ishihara
Published in: Journal of the American Chemical Society (2022)
Here we report the oxidative umpolung of 2,3-disubstituted indoles toward enantioselective dearomative aza-spirocyclization to give the corresponding spiroindolenines using chiral quaternary ammonium hypoiodite catalysis. Mechanistic studies revealed the umpolung reactivity of C3 of indoles by iodination of the indole nitrogen atom. Moreover, the introduction of pyrazole as an electron-withdrawing auxiliary group at C2 suppressed a competitive dissociative racemic pathway, and enantioselective spirocyclization proceeded to give not only spiropyrrolidines but also four-membered spiroazetidines that are otherwise difficult to access.
Keyphrases
  • ionic liquid
  • molecular docking
  • single cell
  • room temperature
  • molecular dynamics
  • capillary electrophoresis
  • mass spectrometry