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Photoredox-Mediated Mono- and Difluorination of Remote Unactivated Methylene C(sp3)-H Bonds of N-Alkyl Sulfonamides.

Zhiqiang DengZhenxiang ZhaoGang HeGong Chen
Published in: Organic letters (2021)
A photoredox-mediated δ-C(sp3)-H fluorination of sulfonyl-protected primary alkylamines with Selectfluor is developed. The reaction can proceed in excellent monofluorination selectivity for amine substrates without α substituent. For α-substituted substrates, a slightly modified reaction conditions with two rounds of operation gives the δ,δ-difluorination products in good yield. Mechanistic studies suggest SET oxidation of sulfonamide group directly generates the key sulfonamide N radical intermediate, which triggers a 1,5-HAT process to form the δ alkyl radical.
Keyphrases
  • visible light
  • ionic liquid
  • molecular docking
  • hydrogen peroxide
  • case control
  • nitric oxide
  • high resolution