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Catalysis Science & Technology
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COMMUNICATION
Journal Name
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control experiments ruled out the possibility through amide
and aldehyde intermediates, it is reasonable that silyl acetal
intermediate may form and act as electrophile to react with
amine to form C‐N bond. As depicted in Figure 2, first, Si‐H
bond is activated on the surface of Pt/C, and formic acid is also
H. T. Clarke, H. B. Gillespie and S. Z. Weisshaus, J. Am. Chem.
DOI: 10.1039/C6CY00674D
Soc., 1933, 55, 4571. (c) P. Tundo and M. Selva, Acc. Chem.
Res., 2002, 35, 706; (d) Y. Zhao, S. W. Foo and S. Saito,
Angew. Chem., Int. Ed., 2011, 50, 3006.
For examples by using hydrosilane as reductant: (a) Y. Li, X.
Fang, K. Junge and M. Beller, Angew. Chem., Int. Ed., 2013,
absorbed on Pt/C (
form disilyl geminal diol ether, and disilyl geminal diol ether
was attacked by absorbed amine ( ). It is worth mentioning
the reason why aliphatic amine is unreactive may be ascribed
to the weak adsorption on Pt/C due to the lack of aromatic
B). Formic acid is reduced by hydrosilane to
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, 9568; (b) O. Jacquet, X. Frogneux, C. D. N. Gomes and T.
Cantat, Chem. Sci., 2013, , 2127; (c) E. Blondiaux, J. Pouessel
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C
and T. Cantat, Angew. Chem., Int. Ed., 2014, 53, 12186; (d) S.
Das, F. D. Bobbink, G. Laurenczy and P. J. Dyson, Angew.
Chem., Int. Ed., 2014, 53, 12876; (e) Z. Yang, H. Zhang, B. Yu,
Y. Zhao, Z. Ma, G. Ji, B. Han and Z. Liu, Chem. Commun., 2015,
51, 11576; (f) Z. Yang, B. Yu, H. Zhang, Y. Zhao, G. Ji, Z. Ma, X.
Gao and Z. Liu, Green Chem., 2015, 17, 4189; (g) T. V. Q.
Nguyen, W.‐J. Yoo, and S. Kobayashi, Adv. Synth. Catal., 2016,
‐
Pt interaction. After forming the C‐N bond by nucleophilic
attack and generation of siloxane, silyl aminomethanol ether
intermediate is formed (
intramolecular nucleophilic attack and generate iminium
cation. Reduction of the iminium intermediate ( ) and
desorption deliver N‐methylation product ( to ). The failure
D). D may release siloxane via
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58, 452.
For examples by using H
Yan, K. Junge and M. Beller, Angew. Chem., Int. Ed., 2013, 52
2156; (b) K. Beydoun, T. v. Stein, J. Klankermayer and W.
E
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as reductant: (a) Y. Li, I. Sorribes, T.
,
F
A
1
of higher carboxylic acids as alkylation reagent may be
attributed to steric hindrance of the silyl acetal intermediate
proposed in this mechanism.
Leitner, Angew. Chem., Int. Ed., 2013, 52, 9554; (c) A. Tlili, X.
Frogneux, E. Blondiaux and T. Cantat, Angew. Chem., Int. Ed.,
2
014, 53, 2543; (d) K. Beydoun, G. Ghattas, K. Thenert, J.
Klankermayer and W. Leitner, Angew. Chem., Int. Ed., 2014,
, 11010; (e) X. Cui, X. Dai, Y. Zhang, Y. Deng and F. Shi,
Chem. Sci., 2014, , 649; (f) X. Cui, Y. Zhang, Y. Deng and F.
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Conclusions
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Shi, Chem. Commun., 2014, 50, 13521; (g) X.‐L. Du, G. Tang,
H.‐L. Bao, Z. Jiang, X.‐H. Zhong, D. S. Su and J.‐Q. Wang,
ChemSusChem., 2015, 8, 3489.
For examples by using other reductant: W.‐C. Chen, J.‐S.
Shen, T. Jurca, C.‐J. Peng, Y.‐H. Lin, Y.‐P. Wang, W.‐C. Shih, G.
In conclusion, we have demonstrated N‐methylation of aniline
and aromatic imine with formic acid as carbon source by using
a commercially available Pt/C catalyst. Both primary aniline
and secondary aniline can be methylated in the presence of
various functional groups including reducible ester, nitro and
cyano substituents. Aromatic imine can also be reduced and
methylated under the same conditions in a cascade manner.
The advantage of this newly described method includes the
operational simplicity, high TON, ready availability of the
catalyst, and also good functional group compatibility.
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P. A. Yap and T.‐Gan Ong, Angew. Chem., Int. Ed., 2015, 54
5207;
,
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1
(a) M. Selva, A. Perosa and M. Fabris, Green Chem., 2008, 10
,
1068; (b) Y. Li, I. Sorribes, C. Vicent, K. Junge and M. Beller,
Chem. Eur. J., 2015, 21, 16759.
0 (a) I. Sorribes, K. Junge and M. Beller, Chem. Eur. J., 2014, 20
,
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878; (b) S. Savourey, G. Lefèvre, J.‐C. Berthet and T. Cantat,
Chem. Commun., 2014, 50, 14033; (c) M.‐C. Fu, R. Shang, W.‐
M. Cheng and Y. Fu, Angew. Chem., Int. Ed., 2015, 54, 9042.
1 (a) L .Deng, J. Li, D. M. Lai, Y. Fu and Q. X. Guo, Angew. Chem.,
Int. Ed., 2009, 48, 6529; (b) S. Enthaler, J. v. Langermann and
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Acknowledgements
We acknowledge the financial support from the National
Natural Science Foundation of China (No. 21304032), the
Natural Science Foundation of Hubei Province of China (No.
T. Schmidt, Energy Environ. Sci., 2010,
3, 1207; (c) W.
Supronowicz, I. A. Ignatyev, G. Lolli, A. Wolf, L. Zhao and L.
Mleczko, Green Chem., 2015, 17, 2904; (d) A. K. Singh, S.
Singh and A. Kumar, Catal. Sci. Technol., 2016, 6, 12.
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2 (a) W. Wang, S. Wang, X. Ma and J. Gong, Chem. Soc. Rev.,
011, 40, 3703; (b) H.‐R. Jhong, S. Ma and P. J. A. Kenis, Curr.
Opin. Chem. Eng., 2013, , 191; (c) Y. Tamaki, K. Koike and O.
Ishitani, Chem. Sci., 2015, , 7213. (d) Z.‐Z, Yang, H. Zhang, B.
Yu, Y. Zhao, G. Ji and Z. Liu, Chem. Commun., 2015, 51, 1271.
3 (a) H. A. Rass, N. Essayem and M. Besson, Green Chem., 2013,
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014CFB570) and Hubei Engineering University.
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