Organic Letters
Letter
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anhydride and 4-dimethylaminopyridine affords O-protected
anilinophenols 37 and 38 in quantitative yields (Scheme 3C).
In conclusion, a highly efficient para-selective oxidative
amination of phenols by primary or secondary anilines
catalyzed by M[TPP]Cl (M = Fe or Mn) complexes was
developed. This reaction provides a direct entry to
benzoquinone anils and N,O-biaryl compounds that are not
readily accessible by any other sustainable method. The
postulated mechanism involves the coupling of a liberated
anilino radical and an iron-ligated (4-R)phenoxyl radical. The
C−N coupling step affords unstable anilinoquinone inter-
mediates that undergo either dehydrogenation (R = H),
elimination (R = OMe), or [3,3]-sigmatropic rearrangement
(R = alkyl), depending on the identity of the phenolic para-
substituent. We intend to continue our group effort in
developing novel catalytic systems for chemo-, regio-, and
stereoselective oxidative aniline coupling reactions.
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ASSOCIATED CONTENT
* Supporting Information
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sı
The Supporting Information is available free of charge at
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Catal. 2017, 7, 2446−2451. (b) Zhao, Y. T.; Huang, B. B.; Yang, C.;
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Experimental procedures and spectroscopic data of all
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(12) Bering, L.; D’Ottavio, L.; Sirvinskaite, G.; Antonchick, A. P.
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AUTHOR INFORMATION
Corresponding Author
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135−145. (b) Genies, E. M.; Boyle, A.; Lapkowski, M.; Tsintavis, C.
Doron Pappo − Department of Chemistry, Ben-Gurion
University of the Negev, Beer-Sheva 84105, Israel;
Synth. Met. 1990, 36 (2), 139−182.
̆
́
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S.; Smrcina, M.; Sticha, M.; Hanus, V.; Polasek, M.; Kocovsky, P. J.
Org. Chem. 1998, 63 (22), 7727−7737.
Author
Vlada Vershinin − Department of Chemistry, Ben-Gurion
University of the Negev, Beer-Sheva 84105, Israel
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Complete contact information is available at:
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
This work was supported by the Israel Science Foundation
(Grant No. 164/16).
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