NDLI: Cu-Catalyzed aromatic C–H imidation with <i>N</i>-fluorobenzenesulfonimide: mechanistic details and predictive models

Content Provider	Royal Society of Chemistry (RSC)
Author	Murakami, Kei Musaev, Djamaladdin G. Itami, Kenichiro Haines, Brandon E. Kuwata, Keiko Kawakami, Takahiro
Copyright Year	2017
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.
Starting Page	988
Ending Page	1001
Page Count	14
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	8
Issue Number	2
Journal	Chemical Science
DOI	10.1039/c6sc04145k
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Subscribed
Subject Keyword	Br Aryl radical Covalent bond Electron transfer Ion NFSI Catalytic cycle
Content Type	Text
Resource Type	Article
Subject	Chemistry

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