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. 2013 Sep 11;135(36):13278-81.
doi: 10.1021/ja4064926. Epub 2013 Sep 3.

Pd-catalyzed aryl C-H imidation with arene as the limiting reagent

Gregory B Boursalian #  1 , Ming-Yu Ngai #  1 , Katarzyna N Hojczyk  1 , Tobias Ritter  1
Affiliations

Pd-catalyzed aryl C-H imidation with arene as the limiting reagent

Gregory B Boursalian et al. J Am Chem Soc. .

Abstract

An amine-N-oxide-ligated palladium complex, in conjunction with a silver cocatalyst, catalyzes imidation of arenes by the reagent N-fluorobenzenesulfonimide. The reaction enables imidation of a variety of arenes at or below room temperature, requires no coordinating directing group on the substrate, and gives synthetically useful yields with only 1 equiv of arene. Mechanistic data implicate an unusual mechanism devoid of commonly invoked organometallic intermediates: oxidation of the Pd catalyst occurs as the turnover-limiting step, while C-H bond functionalization occurs subsequently at a high oxidation state of the catalyst.

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Figures

Figure 1
Figure 1
C–H imidation catalyzed by 1 and Ag(bipy)2ClO4, and x ray structure of the cation of 1 (elipsoids drawn at 50% probability)
Figure 2
Figure 2
Valence orbital diagram of 1
Scheme 1
Scheme 1. Proposed Catalytic Cycle
Scheme 2
Scheme 2. Kinetic Study of Imidation and NFBS Reduction Catalyzed by 1
Scheme 3
Scheme 3. Intramolecular and Intermolecular Kinetic Isotope Effect
See this image and copyright information in PMC

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