Please do not adjust margins
Green Chemistry
Page 6 of 8
ARTICLE
Journal Name
27c
B
r
4-OCH3
4-OCH3
4-CH3
3n
3r
95
Acknowledgements
This work was supported by Natural SDciOeIn: 1c0e.10F3o9u/Cn9dGaCti0o1n99o3Ff
Science and Technology Agency of Shanxi Province
(201801D221068), the Natural Science Foundation of Shanxi
Normal University (ZR1708), and 1331 Project of Shanxi
Province.
28c
B
r
4-OCH3
90
a
Reaction condition: aryl halides (1 mmol), triaylbismuths (0.43
mmol), K2CO3 (4 mmol), solvent (2.5 mL, EtOH:H2O = 4:1), Pd@COF-
NHC (2 mol%) room temperature for 5.0 h; b Isolated yields; c Reflux.
a template under different bases and solvents at room
temperature (Table S5, entries 1-18; Table 3). As shown in Table
S3, reactions of 4-iodonitrobenzene with BiPh3 in DMSO under
different bases led to the corresponding 4-nitrobiphenyls in 21-
56% yields, with K2CO3 gaving the higher yield (Table 3, entry 1;
Table S5, entries 1-5). The catalytic activity of Pd@COF-NHC was
highly dependent on the solvent and reaction time. Reported
cross-coupling reactions of triarylbismuths with aryl halides
were conducted in expensive dry solvents such as NMP, DME,
or DMSO [9a]. In contrast, Pd@COF-NHC allows the reactions to
progress in ethanol aqueous solution at room temperature
within 5.0 h, making it a greener system (Table 3, entry 2; Table
S5, entries 14-18). Therefore, the ethanol aqueous solution was
selected as the optimal solvent.
References
1
C. M. Zinser, K. G. Warren, R. E. Meadows, F. Nahra, A. M. Al-
Majid, A. Barakat, M. S. Islam, S. P. Nolan, C. S. J. Cazin, Green
Chem. 2018, 20, 3246.
2
B. B. Zhang, J. L. Song, H. Z. Liu, J. H. Shi, J. Ma, H. L. Fan, W. T.
Wang, P. Zhang, B. X. Han, Green Chemistry, 2014, 16, 1198; R.
Zhong, A. Pöthig, Y. Feng, K. Riener, W. A. Herrmann, F. E. Kühn,
Green Chemistry, 2014, 16, 4955; S. Paul, M. M. Islam, S. M. Islam,
RSC Advances, 2015, 5, 42193; S. H. Nazari, J. E. Bourdeau, M. R.
Talley, G. A. Valdivia-Berroeta, S. J. Smith, D. J. Michaelis, ACS
Catalysis, 2018, 8, 86; P. Destito, A. Sousa-Castillo, J. R. Couceiro,
F. López, M. A. Correa-Duarte, J. L. Mascareñas, Chemical Science,
2019. 10, 2598.
A. P. Côté, A. I. Benin, N. W. Ockwig, M. O'Keeffe, A. J. Matzger,
O. M. Yaghi, Science, 2005, 310, 1166; J. W. Colson, W. R. Dichtel,
Science, 2011, 332, 228; T. Ma, E. A. Kapustin, S. X. Yin, L. Liang,
Z. Zhou, J. Niu, L. H. Li, Y. Wang, J. Su, J. Li, X. Wang, W. D. Wang,
W. Wang, J. Sun, O. M. Yaghi, Science, 2018, 361, 48; F. Beuerle,
B. Gole, Angew. Chem. Int. Ed., 2018, 57, 4850; Y. Han, M. Zhang,
Y.-Q. Zhang, Z.-H. Zhang, Green Chem., 2018, 20, 4891.
C. D. Wu, M. Zhao, Adv. Master, 2017, 29, 1603945; A. H.
Chughtai, N. Ahmad, H. A. Younus, A. Laypkov, F. Verpoort, Chem.
Soc. Rev., 2015, 44, 6804; C. I. Ezugwu, B. Mousavi, M. A. Asraf,
Z. Luo, F. Verpoort, J. Catal., 2016, 344, 445; S. Li, Y. Wang, Y.
Yang, B. Chen, J. Tai, H. Liu, B. Han, Green Chem. 2019, 10.1039/-
C8GC03529F
3
Using the optimised conditions, the cross-coupling scope
and generality were investigated with a variety of aryl iodides
and triarylbismuths in ethanol aqueous solution at room
temperature for 5.0 h (Table 4, entries 1-19). As shown in Table
4, the excellent catalytic activity of 2 mol% Pd loaded on COF-
NHC was observed under mild conditions regardless of the
presence of electron-withdrawing or electron-donating groups
on phenyl (80-96%). Additionally, the aryl bromides also gave
excellent yield under higher temperatures with a remarkably
broad substrate scope (Table 4, entries 20-28).
4
5
Q. Fang, S. Gu, J. Zheng, Z. Zhuang, S. Qiu, Y. Yan, Angew. Chem.
Int. Ed., 2014, 53, 2878; H. Xu, J. Gao, D. Jiang, Nat. Chem., 2015,
7, 905; X. Wang, X. Han, J. Zhang, X. Wu, Y. Liu, Y. Cui, J. Am. Chem.
Soc., 2016, 138, 12332.
Conclusions
6
7
8
9
S. Y. Ding, J. Gao, Q. Wang, Y. Zhang, W. G. Song, C. Y. Su, W.
Wang, J. Am. Chem. Soc., 2011, 133, 19816.
H. S. Xu, S. Y. Ding, W. K. An, H. Wu, W. Wang, J. Am. Chem. Soc.,
2016, 138, 11489.
G.-H. Ning, Z. Chen, Q. Gao, W. Tang, Z. Chen, C. Liu, B. Tian, X. Li,
K. P. Loh, J. Am. Chem. Soc., 2017, 139, 8897.
X. Zhang, J. Sun, G. Wei, Z. Liu, H. Yang, K. Wang, H. Fei, Angew.
Chem., 2019, 131, 1; S. E. Hooshmand, B. Heidari, R. Sedghi, R. S.
Varma, Green Chem., 2019, 21, 381.
We have developed the N-heterocyclic carbene containing
imine-linked COF and used it to synthesis a stable and
atomically dispersed palladium heterogeneous catalyst
(Pd@COF-NHC). The catalyst exhibited superior activities in
Suzuki-Miyaura coupling reaction at room temperature in
aqueous media with high yield and broad scope, and can be
reused directly at least eitht times without obvious loss of
catalytic activity. Meanwhile, the C-C coupling reactions of aryl 10 W. H. Li, C. Y. Li, H. Y. Xiong, Y. Liu, W. Y. Huang, G. J. Ji, J. Zheng,
H. T. Tang, Y. M. Pan, Y. J. Ding, Angew. Chem. Int. Ed., 2019, 58,
1; K. i. Fujita, R. Tamura, Y. Tanaka, M. Yoshida, M. Onoda, R.
Yamaguchi, ACS Catal., 2017, 7, 7226; A. Dumas, R. Tarrieu, T.
Vives, T. Roisnel, V. Dorcet, O. Baslé, M. Mauduit, ACS Catal.,
2018, 8, 3257.
halides with arylbismuths can be performed in unprecedented
mild conditions for high yields. The structure characterisation
result of Pd@COF-NHC suggests that the palladium is likely to
be fixed firmly in the pores of the COF-NHC framework through
imine-metal-NHC (N-Pd-C) binding interactions, preventing the 11 J. Q. Liu, J. J. Yang, J. F. Li, K. Li, X. D. Xiao, Y. L. Bai, J. W. Wang,
Molecular Catalysis, 2017, 443, 125; J. W. Wang, H. B. Song, Q. S.
Li, F. B. Xu, Z.-Z. Zhang, Inorg. Chim. Acta, 2005, 358, 3653; X. D.
Xiao, Y. L. Bai, J. Q. Liu, J. W. Wang, Tetrahedron Lett., 2016, 57,
3385.
Pd ions from aggregation and leaching. This work presents new
insights into using functional COFs as heterogeneous catalysts
in organic synthesis and green chemistry.
12 J. Liu, L. Chen, H. Cui, J. Zhang, L. Zhang, C. Y. Su, Chem. Soc. Rev.,
2014, 43, 6011; N. Sinha, F. E. Hahn, Acc. Chem. Res., 2017, 50,
2167; G. H. Gunasekar, K. Park, V. Ganesan, K. Lee, N. K. Kim, K.
D. Jung, S. Yoon, Chem. Mater., 2017, 29, 6740; M. B. Lalonde, O.
K. Farha, K. A. Scheidt, J. T. Hupp, ACS Catal., 2012, 2, 1550.
13 N. Huang, P. Wang, M. A. Addicoat, T. Heine, D. Jiang, Angew.
Chem. Int. Ed., 2017, 56, 4982; H. Hu, Q. Yan, M. Wang, L. Yu, W.
Pan, B. Wang, Y. Gao, Chinese J. Catal., 2018, 39, 1437; Z. Li, H. Li,
Conflicts of interest
There are no conflicts to declare.
6 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins