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ChemComm
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DOI: 10.1039/C6CC04570G
COMMUNICATION
Journal Name
bromide (2b) afforded 5b in 70% yield (entry 2). In a similar arylboronic acids under mild reaction conditions. Studies
manner, cinnamyl bromide (2c) reacted with 3a and to aimed at extending the scope of other kind of N-heterocyclic
provide 5c in 65% yield (entry 3). The reaction of 3- carbene metal-moieties containing MOFs and their
bromocyclohexene (2d) with and 3a under the same heterogeneous catalytic behaviours are currently underway in
conditions smoothly proceeded to give the corresponding our laboratory.
1
1
product 5d in 68% yield (entry 4).
We are grateful for financial support from NSFC (Grant Nos.
21475078 and 21271120), 973 Program (Grant Nos.
The scope and generality of the present catalytic reaction can
be further extended to substituted arylboronic acids. Under 2012CB821705 and 2013CB933800) and the Taishan Scholar’s
Construction Project.
the optimized conditions, the combination of
or 2d) with 3-cyanobenzeneboronic acid
fluorobenzeneboronic acid (3c), or 3-methoxybenzeneboronic
acid (3d), or 4-(methoxylcarbonyl)benzeneboronic acid (3e
gave the corresponding o-allylbiphenyl derivatives 5e - 5j in 63
71 yields (entries 5-10), respectively. In all cases,
triphenylene ( ) was always obtained as a by-product (yields,
1
and 2 (2a
, 2b
(
3b), or 4-
Notes and references
)
1
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Copéret, A. Comas-Vives, M. P. Conley, D. P. Estes, A.
Fedorov, V. Mougel, H. Nagae, F. Núñez-Zarur, P. A. Zhizhko,
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-
%
4
22-30 %). The product mixture can be easily separated by
column on silica gel using petroleum ether as the eluent.
2
3
A. Corma, H. García, Chem. Rev., 2002, 102, 3837–3892.
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4
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Fig. 3 Left: Reaction time examination and leaching test for coupling reaction
5
6
7
based on 1, 2a and 3a. Reaction conditions: N2,
B (cat. 1% mol Pd), 1 (0.5 mmol),
2a (0.5 mmol), 3a (0.6 mmol), CsF (1.5 mmol), CH3CN (3 mL). The solid catalyst
was filtrated from the reaction solution after 1 h, whereas the filtrate was
transferred to a new vial and reaction was carried out under the same conditions
for an additional 2 h. Right: recycling catalytic test.
K. Oisaki, Q. Li, H. Furukawa, A. U. Czaja, O. M. Yaghi, J. Am.
Chem. Soc., 2010, 132, 9262-9264.
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(a) H. H. Wenk, M. Winkler, W. Sander, Angew. Chem., Int.
For the three-component coupling reactions,
B also exhibits
a heterogeneous catalytic nature, and it can be recovered by
centrifugation and filtration. After washed with H2O/ethanol
and dried at 90°C in vacuum, it was reused for the next run
under the same reaction conditions. The hot leaching test (Fig.
8
9
3) demonstrated no further reaction took place without
B after
ignition of the three-component cyclotrimerization at 1 h. The
inductively coupled plasma (ICP) measurement indicated that
Ed., 2003, 42, 502–528. (b) H. Pellissier, M. Santelli,
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1522. (e) T. T. Jayanth, M. Jeganmohan, C.-H. Cheng, Org.
the Pb and Pd leaching amount from
respectively, after the cyclic catalysis. This suggested that the
Pd-NHC in is catalytic active sites instead of Pd(II) cation, and
B is ca. 0.018 and 1.8 %,
B
the Pb(II)-framework is an ideal carrier to stabilize the Pd-NHC
species during the catalytic process (ESI). In addition, the XRPD
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patterns of
catalytic cycles indicated that the structural integrity of
well preserved (Fig. S6). As shown in Fig. 3, good conversion of
(89 %) and an ideal yield (66 %) of o-allylbiphenyl product
were still obtained after five catalytic runs (Fig. 3). Although
the catalytic mechanism of is not clear, it is believed to be
the same as those of reported molecular Pd(II)-complex.12
In summary, we report a novel bimetallic generated from a
ligand and Pb(II) under solvothermal conditions. The
obtained bimetallic contains N-heterocyclic tetracarbene
B
and those after being reused for five consective
B
was
1
11 (a) D. Peña, S. Escudero, D. Pérez, E. Guitián, L. Castedo,
Angew. Chem. Int. Ed., 1998, 37, 2659-2661. (b) P. T. Lynett,
K. E. Maly, Org. Lett., 2009, 11, 3726–3729. (c) J.-A. García-
López, M. F. Greaney, Org. Lett., 2014, 16, 2338–2341.
12 (a) T. T. Jayanth, M. Jeganmohan, C.-H. Cheng, J. Org. Chem.,
2004, 69, 8445–8450. (b) Y.-L. Liu, Y. Liang, S.-F. Pi, X.-C.
Huang, J.-H. Li, J. Org. Chem., 2009, 74, 3199–3202.
2
B
A
B
Pd(II)-moiety and it can be a highly efficient heterogeneous
catalyst system for benzyne cyclotrimerization and three-
component coupling reaction of benzyne, allylic bromides and
4 | J. Name., 2012, 00, 1-3
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