ACS Catalysis
Letter
a
Table 4. Substrate Scope of Benzamides
ACKNOWLEDGMENTS
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This research was supported by the Institute for Basic Science
(IBS-R010-D1).
REFERENCES
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a
1 (0.2 mmol) and 2a (0.22 mmol) in 1,2-dichloroethane/HFIP (1:1,
0.66 mL) at 60 °C for 12 h (isolated yields).
substituent (4d). It was revealed that the reactivity was not
significantly deteriorated by the electronic variation of
benzamides (4e−g). As aforementioned, the amination
efficiency was maintained with sterically bulky N-alkyl
substituents of benzamide substrates (4h−i).16
ortho-Aminated benzamide products obtained in this study
were readily converted to synthetically17 and biologically18
valuable compounds according to the literature procedures,
thus furnishing 2-(alkylamino)benzamide or N-alkylanthranilic
acid (eq 1).4h,19
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In conclusion, we have developed an oxidative Cp*Ir(III)-
catalyzed direct C−H amination of arenes using primary
alkylamines as a simple and abundant coupling partner.
Mechanistic studies including a set of stoichiometric oxidation
reactions revealed the critical role of external oxidants on the
amino group insertion step, thus eventually leading to the Ir-
catalyzed inner-sphere catalytic process with primary alkyl-
amines for the first time.
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ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
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S
General experimental procedures; characterization de-
tails; and 1H, 13C, and 19NMR spectra of new compounds
(8) Tran, Roane, and Daugulis recently reported a Cu-catalyzed
direct amination of N-benzoyl-8-aminoquinoline with secondary and
primary amines (4 examples) under rather harsh conditions without
detailed mechanistic descriptions: see ref 7a. In the case of primary
amines, even high loading of copper catalyst (25 mol %) resulted in
moderate to low product yields (20 ∼ 52%).
AUTHOR INFORMATION
Corresponding Author
Notes
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The authors declare no competing financial interest.
(9) See the Supporting Information (SI) for detailed information.
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ACS Catal. 2015, 5, 6665−6669