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Issue 2, 2017
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Cu-Catalyzed aromatic C–H imidation with N-fluorobenzenesulfonimide: mechanistic details and predictive models

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Abstract

The LCuBr-catalyzed C–H imidation of arenes by N-fluorobenzenesulfonimide (NFSI), previously reported by us, utilizes an inexpensive catalyst and is applicable to a broad scope of complex arenes. The computational and experimental study reported here shows that the mechanism of the reaction is comprised of two parts: (1) generation of the active dinuclear CuII–CuII catalyst; and (2) the catalytic cycle for the C–H bond imidation of arenes. Computations show that the LCuIBr complex used in experiments is not an active catalyst. Instead, upon reacting with NFSI it converts to an active dinuclear CuII–CuII catalyst that is detected using HRMS techniques. The catalytic cycle starting from the CuII–CuII dinuclear complex proceeds via (a) one-electron oxidation of the active catalyst by NFSI to generate an imidyl radical and dinuclear CuII–CuIII intermediate, (b) turnover-limiting single-electron-transfer (SET1) from the arene to the imidyl radical, (c) fast C–N bond formation with an imidyl anion and an aryl radical cation, (d) reduction of the CuII–CuIII dinuclear intermediate by the aryl radical to regenerate the active catalyst and produce an aryl-cation intermediate, and (e) deprotonation and rearomatization of the arene ring to form the imidated product. The calculated KIE for the turnover-limiting SET1 step reproduces its experimentally observed value. A simple predictive tool was developed and experimentally validated to determine the regiochemical outcome for a given substrate. We demonstrated that the pre-reaction LCuX complexes, where X = Cl, Br and I, show a similar reactivity pattern as these complexes convert to the same catalytically active dinuclear CuII–CuII species.

Graphical abstract: Cu-Catalyzed aromatic C–H imidation with N-fluorobenzenesulfonimide: mechanistic details and predictive models

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Publication details

The article was received on 15 Sep 2016, accepted on 18 Oct 2016 and first published on 19 Oct 2016


Article type: Edge Article
DOI: 10.1039/C6SC04145K
Citation: Chem. Sci., 2017,8, 988-1001
  • Open access: Creative Commons BY license
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    Cu-Catalyzed aromatic C–H imidation with N-fluorobenzenesulfonimide: mechanistic details and predictive models

    B. E. Haines, T. Kawakami, K. Kuwata, K. Murakami, K. Itami and D. G. Musaev, Chem. Sci., 2017, 8, 988
    DOI: 10.1039/C6SC04145K

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