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COMMUNICATION
21a) at 60 °C for 4 h. The treated MOFs were isolated by
ChemComm
(
Notes and references
1
6
DOI: 10.1039/C9CC06659D
centrifugation and H NMR of the HF/d -DMSO digested MOFs
revealed a substantial amount of 21a trapping, giving nearly 1:1
ratio between 21a and the ligands of the MOFs (Figures S11 and
S12). Furthermore, the incubation experiment using UiO-68-
1
.
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O. Jacquet, X. Frogneux, C. Das Neves Gomes and T. Cantat,
(
NHC)ZnCl
1a revealed no inclusion of the guest molecules in the MOFs.
These two experiments indicated that the carboxylate end group of
1a is preferably coordinated to the Zr(IV)-oxo clusters in the
2
and methyl-4-(methylamino)benzoate (4a) instead of 4.
2
Chem. Sci., 2013, 4, 2127-2137.
5
6
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8
9
1
1
1
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.
MOFs, which may protect the metal–NHC moieties from
carboxylates. Secondly, the selective trapping of carboxylate-based
substrates resulted in a significantly increased yield of 21b over 4b
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O. Santoro, F. Lazreg, Y. Minenkov, L. Cavallo and C. S.
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as catalyzed by UiO-68-(NHC)ZnCl
2
(Table 3, entries 5–8).
.
Thirdly, the high loading of 21a inside the MOF pores (100 eq. 21a
1
32, 8858-8859.
S. V. C. Vummaleti, G. Talarico, S. P. Nolan, L. Cavallo and
A. Poater, Organic Chemistry Frontiers, 2016, , 19-23.
incubation experiment) resulted in partial leaching of ligands (tpdc-
0.
1.
2.
1
NH
2
and NHC-based ligands), as evidenced by H NMR analysis of
3
S. Das, F. D. Bobbink, G. Laurenczy and P. J. Dyson, Angew.
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Chem. Soc. Rev., 2014, 43, 6011-6061.
the supernatant (Figures S10 and S11). The decreased yields over
cycles are likely to be induced by the gradual protonation of
carbene sites. However, if the recycled MOF was treated by a
second-round PSE will again produce 75~92% yield of the N- 13.
C. Pettinari, F. Marchetti, N. Mosca, G. Tosi and A. Drozdov,
Polym. Int., 2017, 66, 731-744.
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methylated product.
1
4.
2
017, 117, 8129-8176.
Table 3. N-methylation using CO
2
and phenylsilane with 15.
Y. Jiang, P. Tan, S.-C. Qi, X.-Q. Liu, J.-H. Yan, F. Fan and
L.-B. Sun, Angew. Chem., 2019, 131, 6672-6676.
K. Sumida, D. L. Rogow, J. A. Mason, T. M. McDonald, E.
D. Bloch, Z. R. Herm, T. H. Bae and J. R. Long, Chem. Rev.,
a
different catalysts.
1
6.
2
012, 112, 724-781.
1
1
7.
8.
Y. Yuan, J. Li, X. Sun, G. Li, Y. Liu, G. Verma and S. Ma,
Chem. Mater., 2019, 31, 1084-1091.
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Aguila, K. Forrest, B. Space and S. Ma, Angew. Chem. Int.
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b
19.
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Entry
Catalyst (5 %)
ZnCl
Substrate
21a
21a
21a
21a
21a
21a
4a
Time (h)
Yield(%)
0
1
2
3
4
5
6
7
2
4
4
CuCl
0
2
2
0.
1.
H. He, J. A. Perman, G. Zhu and S. Ma, Small, 2016, 12
309-6324.
,
UiO-68-NH
2
4
8(1)
6
(IPr)ZnCl
UiO-68-(NHC)ZnCl
UiO-68-(NHC)CuCl
2
4
trace
75(1)
84(2)
21(4)
67(2)
W.-Y. W. Gao, H.; Leng, K.; Sun, Y.; Ma, S., Angew. Chem.
Int. Ed., 2016, 55, 5472-5476.
J. An and N. L. Rosi, J. Am. Chem. Soc., 2010, 132, 5578-
2
4
4
22.
5
579.
UiO-68-(NHC)ZnCl
2
4
2
3.
M. H. Beyzavi, R. C. Klet, S. Tussupbayev, J. Borycz, N. A.
Vermeulen, C. J. Cramer, J. F. Stoddart, J. T. Hupp and O. K.
Farha, J. Am. Chem. Soc., 2014, 136, 15861-15864.
X. H. Liu, J. G. Ma, Z. Niu, G. M. Yang and P. Cheng,
Angew. Chem. Int. Ed. , 2015, 54, 988-991.
P. Z. Li, X. J. Wang, J. Liu, J. S. Lim, R. Zou and Y. Zhao, J.
Am. Chem. Soc., 2016, 138, 2142-2145.
B. An, J. Zhang, K. Cheng, P. Ji, C. Wang and W. Lin, J. Am.
Chem. Soc., 2017, 139, 3834-3840.
X. Zhang, J. Sun, G. Wei, Z. Liu, H. Yang, K. Wang and H.
Fei, Angew. Chem. Int. Ed. , 2019, 58, 2844-2849.
G. L. Fang Huang, Lili Zhao, Haixia Li, and Zhi-Xiang
Wang, J. Am. Chem. Soc., 2010, 132, 12388–12396.
8
UiO-68-(NHC)ZnCl
2
4a
12
a
Reaction conditions: substrate (0.25 mmol), catalyst (5 mol% based on amines),
PhSiH (1.5 mmol), DMA (2 mL), CO (1 atm), 60 ℃, 4 h. Yield determined by
3 2
b
2
2
2
2
2
2
3
3
3
3
4.
5.
6.
7.
8.
9.
0.
1.
2.
3.
1
H-NMR using methanol as an internal standard, three independent trials.
In summary, we have developed a catalytic NHC-MOF
protocol for the efficient and recyclable methylation of amines
2 1
using CO as a C building block. Its performance exceeds that of
the homogeneous reference system in terms of reaction rate and
total TONs. The incorporation of metal–NHC complexes in the
MOFs likely protects the catalytic sites from decomposition upon
H. Li, A. D. Robertson and J. H. Jensen, Proteins, 2004, 55
689-704.
,
carboxylate
methylamino)benzoic acid in one step with high yield. This work
reveals the potential of MOFs for utilizing CO as a C building
treatment,
allowing
N
-methylation
of
K. Y. J. Choi, M. Yoon, S. J. Lee, KwanKim, J. Photoch.
Photobio. A., 2000, 132, 105-114.
L. J. Goossen, N. Rodriguez and K. Goossen, Angew. Chem.
Int. Ed., 2008, 47, 3100-3120.
(
2
1
block, combining the advantages of molecular catalysts with those
of stable inorganic porous matrices.
S. J. Lee, S. W. Han, M. Yoon and K. Kim, Vib. Spectrosc.,
2
000, 24, 265-275.
V. Tantishaiyakul, J. Pharm. Biomed. Anal., 2005, 37, 411-
15.
This work was supported by grants from the National Natural
Science Foundation of China (51772217), the Recruitment of Global
Youth Experts by China and the Science & Technology Commission of
Shanghai Municipality (14DZ2261100).
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| Chem. Commun., 2017, 00, 1-3
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