A General Strategy for Aliphatic C-H Functionalization Enabled by Organic Photoredox Catalysis

J Am Chem Soc. 2018 Mar 28;140(12):4213-4217. doi: 10.1021/jacs.8b00592. Epub 2018 Mar 16.

Abstract

Synthetic transformations that functionalize unactivated aliphatic C-H bonds in an intermolecular fashion offer unique strategies for the synthesis and late-stage derivatization of complex molecules. Herein we report a general approach to the intermolecular functionalization of aliphatic C-H bonds using an acridinium photoredox catalyst and phosphate salt under blue LED irradiation. This strategy encompasses a range of valuable C-H transformations, including the direct conversions of a C-H bond to C-N, C-F, C-Br, C-Cl, C-S, and C-C bonds, in all cases using the alkane substrate as the limiting reagent. Detailed mechanistic studies are consistent with the intermediacy of a putative oxygen-centered radical as the hydrogen atom-abstracting species in these processes.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't

MeSH terms

  • Acridines / chemistry*
  • Alkanes / chemistry*
  • Azides / chemical synthesis*
  • Azides / chemistry
  • Catalysis
  • Molecular Structure
  • Oxidation-Reduction
  • Photochemical Processes

Substances

  • Acridines
  • Alkanes
  • Azides