Jump to main content
Jump to site search


Reagent-dictated site selectivity in intermolecular aliphatic C–H functionalizations using nitrogen-centered radicals

Abstract

The site selectivities of intermolecular, aliphatic C–H bond functionalizations are central to the value of these transformations. While the scope of these reactions continues to expand, the site selectivities remain largely dictated by the inherent reactivity of the substrate C–H bonds. Herein, we introduce reagent-dictated site selectivity to intermolecular aliphatic C–H functionalizations using nitrogen-centered amidyl radicals. Simple modifications of the amide lead to high levels of site selectivity in intermolecular C–H functionalizations across a range of simple and complex substrates. DFT calculations demonstrate that the steric demand of the reacting nitrogen-centered radical is heavily affected by the substitution pattern of the starting amide. Optimization of transition state structures consistently indicated higher reagent-dictated steric selectivities using more hindered amides, consistent with experimental results.

Back to tab navigation

Supplementary files

Publication details

The article was received on 17 Apr 2018, accepted on 12 May 2018 and first published on 14 May 2018


Article type: Edge Article
DOI: 10.1039/C8SC01756E
Citation: Chem. Sci., 2018, Accepted Manuscript
  • Open access: Creative Commons BY license
  •   Request permissions

    Reagent-dictated site selectivity in intermolecular aliphatic C–H functionalizations using nitrogen-centered radicals

    A. Carestia, D. Ravelli and E. Alexanian, Chem. Sci., 2018, Accepted Manuscript , DOI: 10.1039/C8SC01756E

    This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements