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Angewandte
Communications
Chemie
[a]
À
(10 mL) was added. The products were analyzed by an Agilent 7820
Table 3: GO-catalyzed direct C H arylation of benzene with ArX.
GC with a HP-INNOWax capillary column and an Agilent GC-MS.
DFT calculations were performed on the basis of spin polarized
DFT within the generalized gradient approximation (GGA-PBE)
including van der Waals (vdw) interactions, as implemented in the
Vienna Ab Initio Simulation Package (VASP).
Entry
Ar
X
1
Product
Yield [%]
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
4-MeOC6H4
C6H5
I
I
I
I
I
I
I
I
I
I
I
I
Br
Br
Cl
1a
1b
1c
1d
1e
1 f
1g
1h
1i
1j
1k
1l
1m
1n
1o
3a
3b
3c
3d
3e
3 f
3g
3h
3i
87.6
81.6
80.7
71.7
61.9
29.4
84.4
57.5
80.1
52.3
92.4
69.2
7.9
Acknowledgements
4-EtC6H4
4-iPrC6H4
2-MeOC6H4
3-MeOC6H4
4-MeC6H4
2-MeC6H4
3-MeC6H4
1-naphthyl
4-PhC6H4
4-ClC6H4
4-MeOC6H4
C6H5
This work received financial support from the Natural Science
Foundation of China (21173009, 21222306, 91334103, and
21136001) and the 973 Project (2011CB201402,
2013CB933100, and 2013CB733501). Soft X-ray adsorption
measurements were done at the NSRF.
3j
3k
3k
3a
3b
3b
Keywords: arylation · carbon · graphene oxide ·
heterogeneous catalysis
3.2
0
C6H5
How to cite: Angew. Chem. Int. Ed. 2016, 55, 3124–3128
Angew. Chem. 2016, 128, 3176–3180
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iodoanisole (1e; entries 1 and 5). Unexpectedly, 3 f was only
furnished in 29.4% yield from 3-iodoanisole (1 f; entry 6).
This result is not in accordance with literature reports.[8] We
speculate that a combination of electronic and steric effects
decrease the reactivity of 1 f when the methoxy group is
located at the meta position. The coupling of benzene with 1-
iodonapththalene was also less efficient. Surprisingly, 4-
chlorobiphenyl was only formed in 4.5% yield in the reaction
of 4-chloro-1-iodobenzene (1l) with benzene. Instead, a large
amount of para-terphenyl 3k was detected in the reaction
mixture, indicating that dehalogenation had occurred
(entry 12). Aryl bromides and chlorides were also tested,
but gave the desired products in reduced yields (entry 13–15).
The recyclability of these GO catalysts was also tested. After
five cycles, the catalyst had maintained more than 60% of its
original activity, and the catalyst could be easily regenerated
by reoxidation (Figure S6).
In summary, a new nanocarbon-based catalytic system for
À
the direct C H arylation of benzene has been developed. To
the best of our knowledge, this is the first report of
À
carbocatalysis for direct C H arylation with formation of
the coupling products in high yields. However, this work has
also provided insights into the roles of the various functional
groups on nanocarbon materials.
Experimental Section
Materials: Graphitic oxide was generated from natural flake graphite
according to a modified Hummers method.[18] Graphitic oxide was
heated in a quartz tube (H2 flow, 30 mLminÀ1) to 2508C (208CminÀ1
)
to obtain graphene oxide.
Catalytic reaction: ArI (0.4 mmol), catalyst (0.01 g), KOtBu
(1.2 mmol), and benzene (4 mL) were added to a 35 mL glass reactor
sealed with a Teflon lid. The reaction mixture was heated to 1208C for
24 h unless otherwise specified. After cooling to room temperature, n-
dodecane (0.05 g) was added as an internal standard, and then CH2Cl2
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W. L. Chen, P. Tang, W. Z. Li, Z. J. Shi, D. S. Su, J. G. Wang, D.
Ma, ACS Catal. 2014, 4, 1261 – 1266.
Angew. Chem. Int. Ed. 2016, 55, 3124 –3128
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3127