光催化串联反应构建共价有机框架

doi:10.6023/cjoc202407036

摘要/Abstract

开发新型的共价有机框架(COFs)材料构建方法一直是当前的研究热点. 光催化作为一种绿色温和的合成策略, 最近已被应用于COFs的合成中, 但是报道依然非常少. 基于此, 本研究借助光催化, 以苄醇作为起始原料, 通过光催化苄醇氧化与亚胺缩合串联反应, 成功构建了包括TAPB-PDA-COF、TAPT-PDA-COF、TZ-BTCA-COF、COF-LZU1 [TAPB, 1,3,5-三(4-氨基苯基)苯; PDA, 对苯二甲醛; TAPT, 2,4,6-三(4-氨基苯基)-1,3,5-三嗪; TZ, 2,4,6-三(4-氨基苯基)-1,3,5-三嗪; BTCA, 均苯三甲醛]在内的一系列亚胺键连接的COFs. 并且, 利用TZ-BTCA-COF作为光催化剂, 成功实现了光催化硫醚氧化反应, 以良好的收率得到了亚砜产物. 该工作不仅丰富了COFs的光催化合成方法, 而且将COFs的构建单体范围扩展到了苄醇, 为COFs的合成提供了新思路.

关键词: 共价有机框架, 光催化, 串联反应

Developing novel strategies for the construction of covalent organic frameworks (COFs) is always the focus of current research. Recently, the visible-light mediated photocatalysis has been introduced to produce COFs, due to its mild and green characteristics. However, there are still rare reports about the photocatalytic synthesis of COFs. Herein, a series of imine-linked COFs including TAPB-PDA-COF, TAPT-PDA-COF, TZ-BTCA-COF, and COF-LZU1 (TAPB, 1,3,5-tris-(4- aminophenyl)benzene; PDA, terephthalaldehyde; TAPT, 2,4,6-tris(4-aminophenyl)-1,3,5-triazine; TZ, 2,4,6-tris(4-amino- phenyl)-1,3,5-triazine; BTCA, 1,3,5-benzenetricarbaldehyde) were successfully synthesized via the photocatalytic cascade reaction using the benzyl alcohols and amines as the starting materials. The reaction proceeded via the sequential photo- catalytic oxidation of benzyl alcohols and imine condensation steps to generate the imine-linked COFs. Furthermore, the obtained TZ-BTCA-COF was employed as the photocatalyst to promote the photocatalytic oxidation of sulfides, affording sulfoxides in good yields. It is believed that this work not only enriches the photocatalytic synthetic methodology of COFs, but also expands the scope of monomers for COFs synthesis to benzyl alcohols, providing a new way for COFs synthesis.

Key words: covalent organic frameworks, photocatalysis, cascade reaction

引用此文

牛丽菁, 吴成娟, 梁文静, 耿琰, 董育斌. 光催化串联反应构建共价有机框架[J]. 有机化学, 2025, 45(5): 1707-1715.

Lijing Niu, Chengjuan Wu, Wenjing Liang, Yan Geng, Yubin Dong. Construction of Covalent Organic Frameworks via Photocatalytic Cascade Reaction[J]. Chinese Journal of Organic Chemistry, 2025, 45(5): 1707-1715.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 10

图式1. 光催化苄醇氧化与亚胺缩合串联反应

Scheme 1. Photocatalytic benzyl alcohol oxidation and imine condensation cascade reaction

图式2. 光催化苄醇氧化与亚胺缩合串联反应合成COFs

Scheme 2. Synthesis of COFs via photocatalytic benzyl alcohol oxidation and imine condensation cascade reaction

图1. (a) TAPB-PDA-COF, (b) TAPT-PDA-COF, (c) TZ-BTCA-COF和(d) COF-LZU1的傅里叶变换红外光谱图

Figure 1. FT-IR spectra of (a) TAPB-PDA-COF, (b) TAPT-PDA-COF, (c) TZ-BTCA-COF and (d) COF-LZU1

图2. (a) TAPB-PDA-COF, (b) TAPT-PDA-COF, (c) TZ-BTCA-COF和(d) COF-LZU1的X射线粉末衍射图

Figure 2. PXRD patterns of (a) TAPB-PDA-COF, (b) TAPT-PDA-COF, (c) TZ-BTCA-COF and (d) COF-LZU1

图3. (a) TAPB-PDA-COF, (b) TAPT-PDA-COF, (c) TZ-BTCA-COF和(d) COF-LZU1的扫描电子显微镜图像

Figure 3. SEM images of (a) TAPB-PDA-COF, (b) TAPT-PDA-COF, (c) TZ-BTCA-COF and (d) COF-LZU1

图4. (a) TAPB-PDA-COF, (b) TAPT-PDA-COF, (c) TZ-BTCA-COF和(d) COF-LZU1的紫外-可见漫反射光谱图

Figure 4. UV-Vis spectra of (a) TAPB-PDA-COF, (b) TAPT-PDA-COF, (c) TZ-BTCA-COF and (d) COF-LZU1

Entry	TZ-BTCA-COF/mg	Oxidant	Solvent	Yield^b/%
1	6	O₂	EtOH	83
2	6	O₂	MeOH	99
3	6	O₂	CH₃CN	68
4	6	O₂	THF	66
5	6	O₂	CH₂Cl₂	42
6	6	O₂	CHCl₃	60
7	6	O₂	Acetone	43
8	4	O₂	MeOH	96
9	8	O₂	MeOH	98
10^c	6	O₂	MeOH	20
11^d	6	O₂	MeOH	32
12^e	6	O₂	MeOH	N.R.
13	6	Air	MeOH	59
14	6	N₂	MeOH	N.R.
15	—	O₂	MeOH	N.R.

表1. 反应条件优化a

Table 1. Optimization of the reaction conditions

图5. (a)沥出实验和(b)催化循环

Figure 5. (a) Leaching test and (b) the catalytic cycles

表2. 光氧化反应的底物范围a

Table 2. Scope of the photooxidation reaction

图式3. 光氧化反应的机理

Scheme 3. Proposed mechanism of the photooxidation reaction

参考文献 25

[1]	(a) Feng X.; Ding X.; Jiang D. Chem. Soc. Rev. 2012, 41, 6010.
	(b) Ding S.-Y.; Wang W. Chem. Soc. Rev. 2013, 42, 548.
	(c) Diercks C. S.; Yaghi O. M. Science 2017, 355, 1585.
	(d) Wei Y.; Wang J.; Li Y.; Wang T.; Ma S.; Xie L. Acta Chim. Sinica 2024, 82, 75 (in Chinese)
	(魏颖, 王家成, 李玥, 汪涛, 马述威, 解令海, 化学学报, 2024, 82, 75.) doi: 10.6023/A23110507
[2]	Furukawa H.; Yaghi O. M. J. Am. Chem. Soc. 2009, 131, 8875.
[3]	Kan X.; Wang J.-C.; Chen Z.; Du J.-Q.; Kan J.-L.; Li W.-Y.; Dong Y.-B. J. Am. Chem. Soc. 2022, 144, 6681.
[4]	(a) Wei P.-F.; Qi M.-Z.; Wang Z.-P.; Ding S.-Y.; Yu W.; Liu Q.; Wang L.-K.; Wang H.-Z.; An W.-K.; Wang W. J. Am. Chem. Soc. 2018, 140, 4623.
	(b) He M.; Ye Z.; Lin G.; Yin S.; Huang X.; Zhou X.; Yin Y.; Gui B.; Wang C. Acta Chim. Sinica 2023, 81, 784 (in Chinese)
	(何明慧, 叶子秋, 林桂庆, 尹晟, 黄心翊, 周旭, 尹颖, 桂波, 汪成, 化学学报, 2023, 81, 784.) doi: 10.6023/A23040178
[5]	Chen R.; Shi J.-L.; Ma Y.; Lin G.; Lang X.; Wang C. Angew. Chem., Int. Ed. 2019, 58, 6430.
[6]	Lu M.; Liu J.; Li Q.; Zhang M.; Liu M.; Wang J.-L.; Yuan D.-Q.; Lan Y.-Q. Angew. Chem., Int. Ed. 2019, 58, 12392.
[7]	Stegbauer L.; Schwinghammer K.; Lotsch B. V. Chem. Sci. 2014, 5, 2789.
[8]	Li J.; Jing X.; Li Q.; Li S.; Gao X.; Feng X.; Wang B. Chem. Soc. Rev. 2020, 49, 3565.
[9]	(a) Ding H.; Li J.; Xie G.; Lin G.; Chen R.; Peng Z.; Yang C.; Wang B.; Sun J.; Wang C. Nat. Commun. 2018, 9, 5234.
	(b) Haotian R.; Zhu Z.; Cai Y.; Wang W.; Wang Z.; Liang A.; Luo A. Acta Chim. Sinica 2022, 80, 1524 (in Chinese). doi: 10.6023/A22070339
	(浩天瑞霖, 朱子煜, 蔡艳慧, 王微, 王祯, 梁阿新, 罗爱芹, 化学学报, 2022, 80, 1524.) doi: 10.6023/A22070339
[10]	Côte A. P.; Benin A. I.; Ockwig N. W.; O’Keeffe M.; Matzger A. J.; Yaghi O. M. Science 2005, 310, 1166.
[11]	Kuhn P.; Antonietti M.; Thomas A. Angew. Chem., Int. Ed. 2008, 47, 3450.
[12]	Campbell N. L.; Clowes R.; Ritchie L. K.; Cooper A. I. Chem. Mater. 2009, 21, 204.
[13]	Biswal B. P.; Chandra S.; Kandambeth S.; Lukose B.; Heine T.; Banerjee R. J. Am. Chem. Soc. 2013, 135, 5328.
[14]	Yang S.-T.; Kim J.; Cho H.-Y.; Kim S.; Ahn W.-S. RSC Adv. 2012, 2, 10179.
[15]	Dey K.; Pal M.; Rout K. C.; Kunjattu H S.; Das A.; Mukherjee R.; Kharul U. K.; Banerjee R. J. Am. Chem. Soc. 2017, 139, 13083.
[16]	(a) Lang X.; Zhao J.; Chen X. Chem. Soc. Rev. 2016, 45, 3026.
	(b) Chen B.; Wu L.-Z.; Tung C.-H. Acc. Chem. Res. 2018, 51, 2512.
	(c) Huang H.-M.; Bellotti P.; Glorius F. Acc. Chem. Res. 2022, 55, 1135.
	(d) Yu X.-Y.; Chen J.-R.; Xiao W.-J. Chem. Rev. 2021, 121, 506.
[17]	Guan Q.; Zhou L.-L.; Dong Y.-B. Adv. Therap. 2022, 5, 2100177.
[18]	Wu C.-J.; Li X.-Y.; Li T.-R.; Shao M.-Z.; Niu L.-J.; Lu X.-F.; Kan J.-L.; Geng Y.; Dong Y.-B. J. Am. Chem. Soc. 2022, 144, 18750.
[19]	Wang G.-B.; Wang Y.-J.; Kan J.-L.; Xie K.-H.; Xu H.-P.; Zhao F.; Wang M.-C.; Geng Y.; Dong Y.-B. J. Am. Chem. Soc. 2023, 145, 4951.
[20]	Wu C.-J.; Shao M.-Z.; Geng Y.; Dong Y.-B. ChemCatChem 2023, 15, e202300244.
[21]	(a) Liu D. W.; Zhou H. X.; Gu X. Y.; Shen X. Q.; Li P. X. Chin. J. Chem. 2014, 32, 117.
	(b) Lang X.; Zhao J. Chem. Asian J. 2018, 13, 599.
[22]	(a) Smith B. J.; Overholts A. C.; Hwang N.; Dichtel W. R. Chem. Commun. 2016, 52, 3690.
	(b) Gomes R.; Bhanja P.; Bhaumik A. Chem. Commun. 2015, 51, 10050.
	(c) Martín-Illán J. Á.; Rodríguez-San-Miguel D.; Franco C.; Imaz I.; Maspoch D.; Puigmartí-Luis J.; Zamora F. Chem. Commun. 2020, 56, 6704.
	(d) Ding S.-Y.; Gao J.; Wang Q.; Zhang Y.; Song W.-G.; Su C.-Y.; Wang W. J. Am. Chem. Soc. 2011, 133, 19816.
[23]	Chen D.; Chen W.; Zhang G.; Li S.; Chen W.; Xing G.; Chen L. ACS Catal. 2022, 12, 616.
[24]	(a) Gu X.; Li X.; Chai Y.; Yang Q.; Li P.; Yao Y. Green Chem. 2013, 15, 357.
	(b) Ren C.; Fang R.; Yu X.; Wang S. Tetrahedron Lett. 2018, 59, 982.
[25]	(a) Park J. K.; Lee S. J. Org. Chem. 2021, 86, 13790. pmid: 27082825
	(b) Lian P.; Wang K.; Liu H.; Li R.; Li M.; Bao X.; Wan X. Org. Lett. 2023, 25, 7984. pmid: 27082825
	(c) Gan S.; Yin J.; Yao Y.; Liu Y.; Chang D.; Zhu D.; Shi L. Org. Biomol. Chem. 2017, 15, 2647. pmid: 27082825
	(d) Lenstra D. C.; Vedovato V.; Ferrer Flegeau E.; Maydom J.; Willis M. C. Org. Lett. 2016, 18, 2086. doi: 10.1021/acs.orglett.6b00712 pmid: 27082825
	(e) Manesh A. A.; Eshbala F. H.; Hemmati S.; Veisi H. RSC Adv. 2015, 5, 70265. pmid: 27082825