光催化[2+1+2]串联反应合成二氢咪唑及其机理探究

doi:10.3866/PKU.DXHX202212010

Abstract

Abstract:

The introduction of the frontier research in the photocatalysis field is important in the teaching of organic chemistry laboratory. It not only expands students' knowledge of photochemical, multi-component catalytic cascade and free radical reactions, but also deepen students' understanding of nucleophilic reaction mechanism and radical and ionic intermediates. The experiment involves three parts: product preparation, mechanism exploration and experimental expansion of imidazoline compounds, including various organic experimental operations such as anhydrous and anaerobic, reaction monitoring, separation, purification and product characterization.

Key words: Visible photoredox catalysis, Multi-component reaction, Tandem reaction, Divergent synthesis

Kexing Ma, Junjie Yang, Baicheng Chen, Yongwen Shen, Xiuqin Hu, Pengfei Xu. Photocatalytic [2+1+2] Tandem Reactions for the Synthesis of Dihydroimidazole and Its Mechanism Study[J].University Chemistry, 2023, 38(4): 106-115.

Figures/Tables 17

References 18

1	Suzuki, T.; Hidaka, T.; Kumagai, Y.; Yamamoto, M Nat. Immunol 2020, 21, 1486. doi: 10.1038/s41590-020-0802-6
2	Schultz, D. M.; Yoon, T. P Science 2014, 343, 985.
3	Ciamician, G Science 1912, 36, 385. doi: 10.1126/science.36.926.385
4	Bera, M.; Lee, D. S.; Cho, E. J Trends Chem 2021, 3, 877. doi: 10.1016/j.trechm.2021.06.001
5	Zhou, C.; Lei, T.; Wei, X. Z.; Ye, C.; Liu, Z.; Chen, B.; Tung, C. H.; Wu, L. Z J. Am. Chem. Soc 2020, 142, 16805. doi: 10.1021/jacs.0c07600
6	Zhou, Q. Q.; Zou, Y. Q.; Lu, L. Q.; Xiao, W. J Angew. Chem. Int. Ed 2019, 58, 1586. doi: 10.1002/anie.201803102
7	Chen, J.; Guo, H. M.; Zhao, Q. Q.; Chen, J. R.; Xiao, W. J Chem. Commun 2018, 54, 6780. doi: 10.1039/C7CC09871E
8	Bass, P. D.; Guble, D. A.; Judd, T. C.; Williams, R. M Chem. Rev 2013, 113, 6816. doi: 10.1021/cr3001059
9	Davies, J.; Sheikh, N. S.; Leonori, D Angew. Chem. Int. Ed 2017, 56, 13361. doi: 10.1002/anie.201708497
10	Maity, S.; Zheng, N. A Angew. Chem. Int. Ed 2012, 51, 9562. doi: 10.1002/anie.201205137
11	Mehedi, M. S.; Tepe, J. J Adv. Synth. Catal 2020, 362, 4189. doi: 10.1002/adsc.202000709
12	Miyazawa, K.; Koike, T.; Akita, M Chem. Eur. J 2015, 21, 11677. doi: 10.1002/chem.201501590
13	Yu, W. L.; Chen, J. Q.; Wei, Y. L.; Wang, Z. Y.; Xu, P.-F Chem. Commun 2018, 54, 1948. doi: 10.1039/C7CC09151F
14	Chen, J. Q.; Yu, W. L.; Wei, Y. L.; Li, T. H.; Xu, P.-F J. Org. Chem 2017, 82, 243. doi: 10.1021/acs.joc.6b02377
15	Mo, J. N.; Yu, W. L.; Chen, J. Q.; Hu, X. Q.; Xu, P.-F Org. Lett 2018, 20, 4471. doi: 10.1021/acs.orglett.8b01760
16	Yu, W.-L.; Jiang, H.-W.; Yan, L.; Feng, Z.-T.; Luo, Y.-C.; Xu, P.-F Sci. China Chem 2021, 64, 274. doi: 10.1007/s11426-020-9852-8
17	Davies, J.; Morcillo. S. P.; Douglas. J. J.; Leonori, D Chem. Eur. J 2018, 24, 12154. doi: 10.1002/chem.201801655
18	Moon, Y.; Park, B.; Kim, I.; Kang, G.; Shin, S.; Kang, D.; Baik, M.-H.; Hong, S Nat. Commun 2019, 10, 4117. doi: 10.1038/s41467-019-12216-3

试剂名称	纯度	制造商
乙腈	AR	西陇科学股份有限公司
二氯甲烷	AR	成都市科隆化学品有限公司
三乙胺(TEA)	AR	成都市科隆化学品有限公司
四氟硼酸水溶液	> 40%	天津市凯通化学试剂有限公司
1-氨基吡啶碘盐	98%	安徽泽升科技有限公司
4-甲基苯磺酰氯	99%	萨恩化学技术(上海)有限公司
苯乙烯	99.5%	萨恩化学技术(上海)有限公司
三(2, 2’-联吡啶)钌二(六氟磷酸)盐[Ru(bpy)₃(PF₆)₂]	99%	上海毕得医药有限公司

仪器名称	厂家型号	仪器名称	厂家型号
30 W灯筒	京东购买	核磁共振波谱仪	美国布鲁克(Bruker Ascend 400)
旋转蒸发仪	德国海道夫	傅里叶变换红外光谱仪	美国尼高力(Nexus 670)

序号	碱	反应物1和反应物2的摩尔比	萃取	柱层析	溶剂	时间/h	产率/%
1 ^{a, b}	K₂CO₃	1 : 1	+	+	MeCN	6	72
2	DIPEA ^c	1 : 1	+	+	DCM	1	1.6
3	TEA	1 : 1	+	+	EA	1	7.9
4	TEA	1 : 1	+	+	EtOH	1	–
5	TEA	1 : 1	+	+	DMSO	1	–
6 ^b	TEA	1 : 1	+	+	DCM	6	84
7	TEA	1 : 1	–	+	DCM	1	81 ^d
8	TEA	1 : 1	+	–	DCM	3	84
9 ^e	TEA	1 : 2	+	–	DCM	3	81
10 ^f	TEA	2 : 3	+	–	DCM	3	88
11	TEA	1 : 1	+	–	DCM	2	87
12	TEA	1 : 1	+	–	DCM	1	90

序号	溶剂	反应物4和反应物3的摩尔比	光强/W	时间/h	产率/%
1	CH₃CN (dry)	1 : 4	8	3	65
2	CH₃CN (AR)	1 : 4	8	3	61
3	CH₃CN (dry)	1 : 4	18	3	79
4	CH₃CN (dry)	1 : 3	18	3	93
5	CH₃CN (dry)	1 : 2	18	3	79
6	CH₃CN (dry)	2 : 3	18	3	75
7	CH₃CN (dry)	1 : 1	18	3	40
8	CH₃CN (dry)	1 : 3	LED ^a	3	75
9	CH₃CN (dry)	1 : 3	30	3	98
10 ^b	CH₃CN (dry)	1 : 4	25	12	95
11	CH₃CN (AR)	1 : 3	30	1	70
12	CH₃CN (AR)	1 : 3	30	1.5	65
13	CH₃CN (AR)	1 : 3	30	2	88
14	CH₃CN (AR)	1 : 3	30	2.5	92
15	CH₃CN (AR)	1 : 3	30	3	93

序号	光照	光催化剂	TEMPO	氮气保护	产率
1	+	–	–	+	未反应
2	–	+	–	+	未反应
3	+	+	+	+	未反应
4	+	+	–	–	仅检测到产物

Photocatalytic [2+1+2] Tandem Reactions for the Synthesis of Dihydroimidazole and Its Mechanism Study

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Figures/Tables 17

References 18

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必修模块	教学时长/h
N-对甲苯磺酰氨基吡啶四氟硼酸盐的制备	2.5
取代咪唑啉化合物的合成	4
核磁、红外表征	1.5
机理探究实验	3.5
拓展模块(可选择其一)
噁唑啉类化合物的合成	5
氮杂环丙烷类化合物的合成	5
核磁共振氢谱、红外光谱表征	1.5

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