Gram-Scale Synthesis of Polymeric Carbon Nitride-Supported Copper: A Practical Catalyst for Ullmann-Type C—N Coupling Modifying Secondary Pyrimidin-2-amines without Additional Ligand

doi:10.6023/cjoc202009014

Abstract

Cu/polymeric carbon nitride (PCN) can be prepared in 10 g scale by calcining Cu(NO₃)₂ with the melamine precursor at 550 ℃. X-ray photoelectron spectroscopy (XPS) analysis demonstrated that copper in the material was in Cu(I) form and it could catalyze the Ullmann-type C—N coupling reactions of pyrimidin-2-amine derivatives with aryl halides without additional ligand. As a heterogeneous catalyst, the material was recoverable and could be reused for at least five times without deactivation. This material was found to be even more active than traditional Cu(I) catalysts and Pd catalysts, affording an opportunity to develop the efficient and practical novel catalyst reagent for the synthesis of medicines containing pyrimidin-2-amine moieties in pharmaceutical industry.

Key words: polymeric carbon nitride (PCN), copper, catalysis, Ullmann-type C—N coupling reaction, pyrimidin-2-amine

Cite this article

Yangyang Sun, Gang Feng, Chao Chen, Yonghong Liu, Xu Zhang. Gram-Scale Synthesis of Polymeric Carbon Nitride-Supported Copper: A Practical Catalyst for Ullmann-Type C—N Coupling Modifying Secondary Pyrimidin-2-amines without Additional Ligand[J]. Chinese Journal of Organic Chemistry, 2021, 41(3): 1216-1223.

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References 20

[1]	(a) Ruiz-Castillo, P.; Buchwald, S. L. Chem. Rev. 2016, 116, 12564. pmid: 18800130
	(b) Hartwig, J. F. Nature 2008, 455, 314. pmid: 18800130
	(c) Monnier, F.; Taillefer, M. Angew. Chem.. Int. Ed. 2009, 48, 6954. pmid: 18800130
	(d) Dorel, R.; Grugel, C. P.; Haydl, A. M. Angew. Chem.. Int. Ed. 2019, 58, 17118. pmid: 18800130
	(e) Chen, Y.; Jing, X.; Yu, L. Chin. J. Org. Chem. 2020, 40, 2570. (in Chinese) pmid: 18800130
	(陈颖, 景崤壁, 俞磊, 有机化学, 2020, 40, 2570.) pmid: 18800130
[2]	(a) Chen, T.; Yan, M.; Zheng, C.; Yuan, J.; Xu, S.; Chen, R.; Huang, W. Chin. J. Chem. 2015, 33, 961. pmid: 31682120
	(b) Bhunia, S.; Vijay Kumar, S.; Ma, D. J. Org. Chem. 2017, 82, 12603. pmid: 31682120
	(b) Ohyoshi, T.; Akemoto, K.; Taniguchi, A.; Ishihara, T.; Kigoshi, H. New J. Chem. 2019, 43, 18442. pmid: 31682120
	(c) Garcia, R. C.; Pech, M. J.; Sommer, R.; Gorman, C. B. J. Org. Chem. 2019, 84, 15079. pmid: 31682120
	(d) Thomas, G. T.; Janusson, E.; Zijlstra, H. S.; McIndoe, J. S. Chem. Commun. 2019, 55, 11727. pmid: 31682120
	(e) Hemmati, S.; Kamangar, S. A.; Yousefi, M.; Salehi, M. H.; Hekmati, M. Appl. Organomet. Chem. 2020, 34, e5611. pmid: 31682120
	(f) Ge, X.; Ge, M.; Chen, X.; Qian, C.; Liu, X.; Zhou, S. Mol. Catal. 2020, 484, 110726. pmid: 31682120
[3]	Zhang, X.; Sun, J.; Chen, T.; Yang, C.; Yu, L. Synlett 2016, 27, 2233.
[4]	Erickson, G.; Guo, J.; McClure, M.; Mitchell, M.; Salaun, M.; Whitehead, A. Tetrahedron Lett. 2014, 55, 6007.
[5]	Maskrey, T. S.; Kristufek, T.; LaPorte, M. G.; Nyalapatla, P. R.; Wipf, P. Synlett 2019, 30, 471.
[6]	(a) Yang, T.; Yin, L.; He, M.; Wei, W.; Cao, G.; Ding, X.; Wang, Y.; Zhao, Z.; Yu, T.; Zhao, H.; Zhang, D. Chem. Commun. 2019, 55, 14343. pmid: 25700130
	(b) Sun, J.; Hu, J.; Han, J.; Yuan, G.; Guo, R. Langmuir 2019, 35, 12704. pmid: 25700130
	(c) Zou, L.; Hou, C.; Liu, Z.; Pang, H.; Xu, Q. J. Am. Chem. Soc. 2018, 140, 15393. pmid: 25700130
	(d) Cheng, Z.; Sun, W. Chin. Chem. Lett. 2016, 27, 81. pmid: 25700130
	(e) Dao, T. D.; Han, G.; Arai, N.; Nabatame, T.; Wada, Y.; Hoang, C. V.; Aono, M.; Nagao, T. Phys. Chem. Chem. Phys. 2015, 17, 7395. pmid: 25700130
[7]	(a) Zhang, D.; Wei, Z.; Yu, L. Sci. Bull. 2017, 62, 1325.
	(b) Chen, C.; Cao, K.; Wei, Z.; Zhang, Q.; Yu, L. Mater. Lett. 2018, 226, 63.
[8]	(a) Yu, L.; Han, Z.; Ding, Y. Org. Process Res. Dev. 2016, 20, 2124. pmid: 26274575
	(b) Yu, L.; Huang, Y.; Wei, Z.; Ding, Y.; Su, C.; Xu, Q. J. Org. Chem. 2015, 80, 8677. pmid: 26274575
[9]	(a) Cao, H.; Yang, Y.; Chen, X.; Liu, J.; Chen, C.; Yuan, S.; Yu, L. Chin. Chem. Lett. 2020, 31, 1887.
	(b) Yang, Y.; Li, M.; Cao, H.; Zhang, X.; Yu, L. Mol. Catal. 2019, 474, 110450.
	(c) Wang, F.; Xu, L.; Sun, C.; Yu, L.; Xu, Q. Appl. Organomet. Chem. 2018, 32, e4505.
	(d) Wang, Y.; Wu, Z.; Li, Q.; Zhu, B.; Yu, L. Catal. Sci. Technol. 2017, 7, 3747.
	(e) Wang, F.; Xu, L.; Huang, J.; Wu, S.; Yu, L.; Xu, Q.; Fan, Y. Mol. Catal. 2017, 432, 99.
[10]	(a) Yang, Y.; Xu, B.; He, J.; Shi, J.; Yu, L.; Fan, Y. Appl. Catal.. A 2020, 590, 117353. doi: 10.1016/j.apcata.2019.117353
	(b) Yang, Y.; Xu, B.; He, J.; Shi, J.; Yu, L.; Fan, Y. Appl. Organomet. Chem. 2019, 33, e5204.
	(c) Zhou, H.; Gong, J.; Xu, B.; Yu, L.; Fan, Y. Appl. Catal.. A 2016, 527, 30.
[11]	(a) Tong, Q.; Zhao, S.; Liu, Y.; Xu, B.; Yu, L.; Fan, Y. Appl. Organomet. Chem. 2020, 34, e538.
	(b) Zhao, S.; Xu, B.; Yu, L.; Fan, Y. Chin. Chem. Lett. 2018, 29, 884.
	(c) Zhao, S.; Xu, B.; Yu, L.; Fan, Y. Chin. Chem. Lett. 2018, 29, 475.
[12]	(a) Liu, C.; Mao, J.; Zhang, X.; Yu, L. Catal. Commun. 2020, 133, 105828.
	(b) Chen, X.; Mao, J.; Liu, C.; Chen, C.; Cao, H.; Yu, L. Chin. Chem. Lett. 2020, 31, 3205.
	(c) Deng, S.; Meng, T.; Xu, B.; Gao, F.; Ding, Y.; Yu, L.; Fan, Y. ACS Catal. 2016, 6, 5807.
	(d) Deng, S.; Zhuang, K.; Xu, B.; Ding, Y.; Yu, L.; Fan, Y. Catal. Sci. Technol. 2016, 6, 1772.
	(e) Tong, Q.; Zong, A.; Gong, W.; Yu, L.; Fan, Y. RSC Adv. 2016, 6, 86663.
[13]	(a) Xia, Y.-T.; Wu, J.-J.; Zhang, C.-Y.; Mao, M.; Ji, Y.-G.; Wu, L. Org. Lett. 2019, 21, 6383. pmid: 31356086
	(b) Xia, Y.-T.; Xie, X.-Y.; Cui, S.-H.; Ji, Y.-G.; Wu, L. Chem. Commun. 2019, 55, 11699. pmid: 31356086
	(c) Xia, Y.-T.; Ma, J.; Wang, X.-D.; Yang, L.; Wu, L. Catal. Sci. Technol. 2017, 7, 5515. pmid: 31356086
	(d) Zhang, Y.; Zhu, J.; Xia, Y.-T.; Sun, X.-T.; Wu, L. Adv. Synth. Catal. 2016, 358, 3039. doi: 10.1002/adsc.v358.19 pmid: 31356086
[14]	(a) Wang, Y.; Wang, X.; Antonietti, M. Angew. Chem.. Int. Ed. 2012, 51, 68.
	(b) Yang, H.; Xu, B.; Yuan, S.; Zhang, Q.; Zhang, M.; Ohno, T. Appl. Catal., B 2019, 243, 513.
	(c) Cao, K.; Deng, X.; Chen, T.; Zhang, Q.; Yu, L. J. Mater. Chem. A 2019, 7, 10918.
	(d) Fan, X.; Yao, Y.; Xu, Y.; Yu, L.; Qiu, C. ChemCatChem 2019, 11, 2596.
[15]	(a) Liu, Y.; Wang, J.-P. Org. Biomol. Chem. 2011, 9, 6873. pmid: 26664644
	(b) Wan, J.-P.; Jing, Y. Beilstein J. Org. Chem. 2015, 11, 2209. doi: 10.3762/bjoc.11.240 pmid: 26664644
	(c) Li, X.; Lin, J.; Wang, J.; Li, Z.; Gu, Q.; Liu, X. Acta Chim. Sinica 2018, 76, 878. (in Chinese) pmid: 26664644
	(李雪飞, 林进顺, 王建, 李忠良, 顾强帅, 刘心元, 化学学报, 2018, 76, 878.) pmid: 26664644
	(d) Duan, X.; Liu, N.; Wang, J.; Ma, J. Chin. J. Org. Chem. 2019, 39, 661. (in Chinese) pmid: 26664644
	(段希焱, 刘宁, 王佳, 马军营, 有机化学, 2019, 39, 661.) pmid: 26664644
	(e) Xie, J.; Wang, X.; Wu, F.; Zhang, J. Chin. J. Org. Chem. 2019, 39, 3026. (in Chinese) pmid: 26664644
	(谢建伟, 汪小创, 吴丰田, 张洁, 有机化学, 2019, 39, 3026.) pmid: 26664644
	(f) Cai, Q.; Zhou, W. Chin. J. Chem. 2020, 38, 879. pmid: 26664644
	(g) Luo, T.; Wan, J.-P.; Liu, Y. Org. Chem. Front. 2020, 7, 1107. pmid: 26664644
	(h) vali, Shaik, B.; Seelam,, M.; Tamminana,, R.; Kammela,, P. R. Tetrahedron 2019, 75, 3865. pmid: 26664644
	(i) Yao, D.; Zhang, J.; Xu, L. Chin. J. Org. Chem. 2020, 40, 1673. (in Chinese) pmid: 26664644
	(姚丹丹, 张金利, 徐亮, 有机化学, 2020, 40, 1673.) pmid: 26664644
	(j) Chen, C.; Cao, Z.; Zhang, X.; Li, Y.; Yu, L.; Jiang, X. Chin. J. Chem. 2020, 38, 1045. pmid: 26664644
	(k) Fan, X.; Yi, R.; Wang, F.; Zhang, X.; Xu, Q.; Yu, L. Chin. J. Org. Chem. 2018, 38, 2736. (in Chinese) pmid: 26664644
	(范昕, 易容, 王芳, 张旭, 徐清, 俞磊, 有机化学, 2018, 38, 2736.) pmid: 26664644
[16]	(a) Zhang, J.; Cao, K.; Zhang, X.; Zhang, Q. Appl. Organomet. Chem. 2020, 34, e5377.
	(b) Cao, H.; Sun, Y.; Wang, F.; Zhang, X. Microporous Mesoporous Mater. 2020, 295, 109972.
[17]	(a) Scott, S. L. ACS Catal. 2018, 8, 8597.
	(b) Duong, U. T.; Gade, A. B.; Plummer, S.; Gallou, F.; Handa, S. ACS Catal. 2019, 9, 10963. doi: 10.1021/acscatal.9b04175
[18]	Wang, M.; Cheng, X.; Ni, Y. Dalton Trans. 2019, 48, 823. doi: 10.1039/c8dt03572e pmid: 30534772
[19]	(a) Chen, C.; Cao, Y.; Wu, X.; Cai, Y.; Liu, J.; Xu, L.; Ding, K.; Yu, L. Chin. Chem. Lett. 2020, 31, 1078.
	(b) Chen, Y.; Deng, X.; Jing, X.; Zhou, H. Chin. J. Org. Chem. 2020, 40, 4147. (in Chinese)
	(陈颖, 邓鑫, 景崤壁, 周宏伟, 有机化学, 2020, 40, 4147.)
	(c) Zheng, Y.; Wu, A.; Ke, Y.; Cao, H.; Yu, L. Chin. Chem. Lett. 2019, 30, 937.
	(d) Zhang, H.; Han, M.; Yang, C.; Yu, L.; Xu, Q. Chin. Chem. Lett. 2019, 30, 263.
[20]	(a) Johansson Seechurn, C. C. C.; Parisel,, S. L.; Colacot,, T. J. J. Org. Chem. 2011, 76, 7918. pmid: 28833674
	(b) Elbert, B. L.; Farley, A. J. M.; Gorman, T. W.; Johnson, T. C.; Genicot, C.; Lallemand, B.; Pasau, P.; Flasz, J.; Castro, J. L.; MacCoss, M.; Paton, R. S.; Schofield, C. J.; Smith, M. D.; Willis, M. C.; Dixon, D. J. Chem.-Eur. J. 2017, 23, 14733. doi: 10.1002/chem.201703931 pmid: 28833674

Entry	Solvent	Base	T/℃	Yield^b/%
1	t-BuOH	t-BuOK	80	23
2	EtOH	t-BuOK	80^c	20
3	THF	t-BuOK	80^c	22
4	1,4-Dioxane	t-BuOK	80	28
5	Toluene	t-BuOK	80	16
6	1,4-Dioxane	KOH	80	20
7	1,4-Dioxane	NaOH	80	16
8	1,4-Dioxane	Pyridine	80	18
9	1,4-Dioxane	t-BuOK	90	45
10	1,4-Dioxane	t-BuOK	100	67
11	1,4-Dioxane	t-BuOK	110^c	82
12	1,4-Dioxane	t-BuOK	120^c	80
13^d	1,4-Dioxane	t-BuOK	110^c	44

Entry	Solvent	Base	T/℃	Yield^b/%
1	t-BuOH	t-BuOK	80	23
2	EtOH	t-BuOK	80^c	20
3	THF	t-BuOK	80^c	22
4	1,4-Dioxane	t-BuOK	80	28
5	Toluene	t-BuOK	80	16
6	1,4-Dioxane	KOH	80	20
7	1,4-Dioxane	NaOH	80	16
8	1,4-Dioxane	Pyridine	80	18
9	1,4-Dioxane	t-BuOK	90	45
10	1,4-Dioxane	t-BuOK	100	67
11	1,4-Dioxane	t-BuOK	110^c	82
12	1,4-Dioxane	t-BuOK	120^c	80
13^d	1,4-Dioxane	t-BuOK	110^c	44

Entry	Ar	X	R	3	Yield^b/%
1	Ph	I	Me	3a	82
2	4-FC₆H₄	I	Me	3b	60
3	4-ClC₆H₄	I	Me	3c	90
4	4-BrC₆H₄	I	Me	3d	72
5	4-MeC₆H₄	I	Me	3e	88
6	3,4-(Me)₂C₆H₃	I	Me	3f	65
7	4-MeOC₆H₄	I	Me	3g	80
8	3-MeOC₆H₄	I	Me	3h	80
9	2-MeOC₆H₄	I	Me	3i	75
10	4-PhC₆H₃	I	Me	3j	65
11	2-C₁₀H₇	I	Me	3k	98
12		I	Me	3l	92
13	4-(4-IC₆H₄)C₆H₄	I	Me	3m	60
14	4-MeOC₆H₄	I	PhCH₂^c	3n	53
15	Ph	Br	Me	3a	56, 60^d
16	4-ClC₆H₄	Br	Me	3c	68^d
17	4-MeC₆H₄	Br	Me	3e	52^d
18	Ph	Cl	Me	3a	26, 30^d

Entry	Ar	X	R	3	Yield^b/%
1	Ph	I	Me	3a	82
2	4-FC₆H₄	I	Me	3b	60
3	4-ClC₆H₄	I	Me	3c	90
4	4-BrC₆H₄	I	Me	3d	72
5	4-MeC₆H₄	I	Me	3e	88
6	3,4-(Me)₂C₆H₃	I	Me	3f	65
7	4-MeOC₆H₄	I	Me	3g	80
8	3-MeOC₆H₄	I	Me	3h	80
9	2-MeOC₆H₄	I	Me	3i	75
10	4-PhC₆H₃	I	Me	3j	65
11	2-C₁₀H₇	I	Me	3k	98
12		I	Me	3l	92
13	4-(4-IC₆H₄)C₆H₄	I	Me	3m	60
14	4-MeOC₆H₄	I	PhCH₂^c	3n	53
15	Ph	Br	Me	3a	56, 60^d
16	4-ClC₆H₄	Br	Me	3c	68^d
17	4-MeC₆H₄	Br	Me	3e	52^d
18	Ph	Cl	Me	3a	26, 30^d

聚合物氮化碳负载铜克级制备一种无需额外配体即可催化二级嘧啶-2-胺的碳-氮乌尔曼偶联反应的实用催化剂