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ChemComm
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COMMUNICATION
Journal Name
Yield (%)
m-NOC-600
m-NOC-800
2, 1108-1117.
DOI: 10.1039/C9CC06793K
O
CN
N
NH2
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CN
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NH2
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N
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O
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NH2
O
NH2
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NH2
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F
F
F
F
O
CN
N
N
NH2
Cl
Cl
Cl
Br
Cl
Br
O
CN
NH2
O
Cl
Cl
Cl Cl
N
CN
NH2
Br
Br
O
CN
N
Br Br
N
NH2
Br
O
Br
CN
NH2
F3
C
F3C
F3
C
CF3
O
S
S
S
S
N
CN
NH2
Fig.
5 Imines and nitriles synthesis over m-NOC-600 and m-NOC-800. Reaction
conditions: 0.5 mmol benzylamine, 60mg catalyst, 2 bar O2.
and Scheme S2 displayed possible reaction pathway. The
reaction course with 2a used as substrate in Fig. S9 further
confirmed 2a intermediates and finally, 89.1% yield of 3a was
obtained under the standard conditions (Scheme S1b).
Fig. 5 showed data for aerobic oxidation of various
substituted benzylamines (see Table S2 and S3 for detailed
data) on m-NOC-600 and m-NOC-800 catalysts, respectively. In
the presence of m-NOC-600 catalyst, it was highly selective for
the imines, whereas it swung to the corresponding nitriles with
amides as another aldehyde ammoxidation product over m-
NOC-800 catalyst. In detail, benzylamine derivatives bearing
electron-donating groups gave the corresponding nitriles in
moderate to high yields as well as those bearing electron-
withdrawing groups. Even for heterocyclic aromatic amines
such as thiophen-3-ylmethanamine, m-NOC-600 and m-NOC-
800 successfully achieved 87% imines and 83.3% nitriles
separately. Unfortunately, aliphatic amines such as octylamine
could not be converted accordingly.
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In summary, we have succeeded in employing a N, O-doped
mesoporous carbon as the first efficient metal-free catalyst for
the aerobic selective oxidation of primary amines to nitriles
under molecular oxygen. Beyond that, the m-NOC at 600oC and
o
800 C can achieve successfully the switch between imine and
nitrile products. The transformation of imine intermediate to
nitriles stems from the C-O group with neighbouring N
environment on the surface. More attempts to explore the
application of carbocatalysts in synthetic transformation is on
the way, broadening the field of metal-free catalysis.
Financial support from Natural Science Foundation of
Liaoning Province (20180540080) and National Natural Science
Foundation of China (21773232, 21902151).
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2015, 54, 4105-4109; (b) Y.-C. Chiang, W.-H. Lin and Y.-C. Chang,
Appl. Surf. Sci., 2011, 257, 2401-2410.
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Enoki, Y. J. Chabal and K. Ping Loh, Nat. Commun., 2012, 3, 1298.
Conflicts of interest
There are no conflicts to declare.
Notes and references
4 | J. Name., 2012, 00, 1-3
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