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Organic & Biomolecular Chemistry
Page 4 of 4
DOI: 10.1039/C8OB01749B
COMMUNICATION
Journal Name
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and X. Li, Org. Lett., 2014, 16, 772−775; (e) D. Yu, C.-S. Wang,
C. Yao, Q. Shen and L. Lu, Org. Lett., 2014, 16, 5544−5547; (f)
H. Saijo, H. Sakaguchi, M. Ohashi and S. Ogoshi,
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Scheme 3 Plausible reaction mechanism.
without considerable impact. These results can excluded the radical
pathway of the amination reaction (Scheme 2d). Meanwhile, the
desired product 3k’ was not detected by using the fluorobenzene
1a’’ as the starting material. Even though we increased reaction
temperatures, only trace product 3k’ was obtained These results
showed that the para-substituents of carbonyl group on the
benzene ring was necessary (Scheme 2e).11
Base on the above results and the literature reports,12 a plausible
mechanism containing an oxidative coupling process is illustrated in
Scheme 3 for the reaction. At the beginning, the oxidative addition
of 4-fluoroacetophenone to the Ag(I) center affords the Ag(II)
intermediate I in the presence of K2S2O8. Subsequently, the Ag(II)
intermediate II is generated through the replace of fluorine atom in
the Ag(II) complex I with the morpholine. Finally, the reductive
elimination step furnishes the product 3a and regenerates the
active Ag(I) species.
C. Feng and T.-P. Loh, J. Am. Chem. Soc., 2017, 139
,
1762−1765; (h) J. Wei, K.-M. Liu and X.-F. Duan, J. Org. Chem.,
2017, 82, 1291−1300; (i) K. Chen, N. Berg, R. Gschwind and B.
König, J. Am. Chem. Soc., 2017, 139, 18444−18447.
For the transition-metal-mediated borylation of fluoroarenes
via C−F bond cleavage, see: (a) T. Niwa, H. Ochiai, Y.
4
Watanabe and T. Hosoya, J. Am. Chem. Soc., 2015, 137
,
4313−14318; (b) J. Zhou, M. W. Kuntze-Fechner, R.
Bertermann, U. S. D. Paul, J. H. J. Berthel, A. Friedrich, Z. Du,
T. B. Marder and U. Radius, J. Am. Chem. Soc., 2016, 138
5250−5253; (c) T. Niwa, H. Ochiai and T. Hosoya, ACS Catal.,
2017, , 4535−4541.
,
7
5
6
For the transition-metal-catalyzed activation of C-F bonds to
construct the C-H bond, see: (a) S. Kuhl, R. Schneider and Y.
Fort, Adv. Synth. Catal., 2003, 345, 341−344;(b) H. Lv, J.-H.
Zhan, Y.-B. Cai, Y. Yu, B. Wang and J.-L. Zhang, J. Am. Chem.
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(d) H. Nakai, K. Jeong, T. Matsumoto and S. Ogo,
In summary, we have developed
a novel Ag-catalyzed
intermolecular amination of fluoroarenes with good regioselectivity.
In this transformation, various substitutions on the phenyl ring of
fluoroarenes can be well tolerated, thus providing a series of
functionalized 4-carbonyl arylamines were obtained in good to
excellent yields. Control experiments showed that the reaction was
accelerated by using a small amount of water. Further studies on
the mechanism and exploit possible synthetic applications of
fluoroarenes by C−F bond cleavage are in progress in our laboratory.
Organometallics, 2014, 33, 4349
−4352.
For the nickel-catalyzed anamination reaction of
fluoroarenes with amines, see: (a) F. Zhu and Z.-X. Wang,
Adv. Synth. Catal., 2013, 355, 3694–3702; (b) T. Harada, Y.
Ueda, T. Iwai and M. Sawamura, Chem. Commun., 2018, 54
1718−1721.
,
7
8
T. Fujita, Y.Watabe, S. Yamashita, H. Tanabe, T. Nojima and J.
Ichikawa, Chem. Lett., 2016, 45, 964−966.
(a) K. Wang, X. Bi, S. Xing, P. Liao, Z. Fang, X. Meng, Q. Zhang,
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H. Yuan, Y. Liu, Z. Tong, H. Li, J. Yang, B.-D. Barry, J. Liu, P.
Conflicts of interest
There are no conflicts to declare.
Liao, J. Zhang, Q. Liu and X. Bi, Chem. Commun., 2012, 48
8802–8804; (c) J. Liu, Z. Fang, Q. Zhang, Q. Liu and X. Bi,
,
Acknowledgements
Angew. Chem., Int. Ed., 2013, 125, 7091–7095; (d) Z. Fang, Y.
,
The authors wish to thank the Natural Science Foundation of
China (21506017), the Natural Science Foundation of Jiangsu
Province (BK20150258), the Joint Innovation Project for
Production-Study-Research in Jiangsu Province (BY2016066-
03).
Feng, H. Dong, D. Li and T. Tang, Chem. Commun., 2016, 52
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9
(a) Q.-Z. Zheng and N. Jiao, Chem. Soc. Rev., 2016, 45, 4590-
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,
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Notes and references
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3
For the transition-metal-catalyzed activation of C-F bonds to
construct the C-C bond, see: (a) H. L. Buckley, T. Wang, O.
4 | J. Name., 2012, 00, 1-3
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