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Organocatalytic nitrenoid transfer: metal-free selective intermolecular C(sp3)–H amination catalyzed by an iminium salt

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Abstract

This report details the first organocatalytic method for nitrenoid transfer and its application to intermolecular, site-selective C(sp3)–H amination. The method utilizes a trifluoromethyl iminium salt as the catalyst, iminoiodinanes as the nitrogen source, and substrate as the limiting reagent. Activated, benzylic, and aliphatic substrates can all be selectively functionalized in yields up to 87%. A mechanistic proposal for the observed reactivity supported by experimental evidence invokes the intermediacy of a diaziridinium salt or related organic nitrenoid, species that have not been previously explored for the purpose of C–H amination. Finally, examples of late-stage functionalization of complex molecules highlight the selectivity and potential utility of this catalytic method in synthesis.

Graphical abstract: Organocatalytic nitrenoid transfer: metal-free selective intermolecular C(sp3)–H amination catalyzed by an iminium salt

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Publication details

The article was received on 10 Sep 2017, accepted on 26 Nov 2017 and first published on 27 Nov 2017


Article type: Edge Article
DOI: 10.1039/C7SC03968A
Citation: Chem. Sci., 2018, Advance Article
  • Open access: Creative Commons BY-NC license
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    Organocatalytic nitrenoid transfer: metal-free selective intermolecular C(sp3)–H amination catalyzed by an iminium salt

    L. A. Combee, B. Raya, D. Wang and M. K. Hilinski, Chem. Sci., 2018, Advance Article , DOI: 10.1039/C7SC03968A

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