光催化有机胺参与的卤原子转移中间体的电子自旋共振(EPR)研究及其应用

doi:10.6023/cjoc202502030

有机化学 ›› 2025, Vol. 45 ›› Issue (10): 3866-3872.DOI: 10.6023/cjoc202502030 上一篇下一篇

研究论文

光催化有机胺参与的卤原子转移中间体的电子自旋共振(EPR)研究及其应用

金炜俊, 任钶, 张光露, 蒋敏^*()

杭州师范大学材料与化学化工学院杭州 311121

收稿日期:2025-02-25 修回日期:2025-04-23 发布日期:2025-05-20
基金资助:
杭州师范大学国内访问学者(4095C5022521106)

Electron Paramagnetic Resonance (EPR) Studies of Photocatalytic Halogen Atom Transfer Intermediates Involving Organic Amines and Its Applications

Weijun Jin, Ke Ren, Guanglu Zhang, Min Jiang^*()

School of Material, Chemistry and Chemical Engineering, University of Hangzhou Normal University, Hangzhou 421001

Received:2025-02-25 Revised:2025-04-23 Published:2025-05-20
Contact: *jiang-m18@hznu.edu.cn
Supported by:
Domestic Visiting Fellows Program of Hangzhou Normal University(4095C5022521106)

文章分享

1. 0253-2786-45-10-3866S.pdf(6285KB)

摘要/Abstract

使用电子自旋共振(EPR)对有机胺参与的光催化卤原子转移(XAT)反应进行原位监测, 得到了催化剂中间态、胺烷基自由基和卤代烃脱卤生成碳中心自由基等中间体的动态转化信息, 并指导实现了光催化单线态氧促进的卤原子转移喹喔啉酮类物质烷基化反应.

关键词: 电子自旋共振(EPR), 反应中间体, 卤原子转移(XAT), 光催化, 烷基化

In situ electron paramagnetic resonance (EPR) monitoring of the photocatalytic halogen atom transfer (XAT) reaction with organic amines has provided insights into the dynamic transformations of intermediates, including catalyst intermediate states, amine alkyl radicals, and the dehalogenation of halogenated hydrocarbons to form carbon-centered radicals. This approach facilitated the photocatalytic single-linear state oxygen-promoted halogen atom transfer quinoxalinone alkylation reaction.

Key words: electron paramagnetic resonance (EPR), reaction intermediates, halogen atom transfer (XAT), photocatalyst, alkylation

引用此文

金炜俊, 任钶, 张光露, 蒋敏. 光催化有机胺参与的卤原子转移中间体的电子自旋共振(EPR)研究及其应用[J]. 有机化学, 2025, 45(10): 3866-3872.

Weijun Jin, Ke Ren, Guanglu Zhang, Min Jiang. Electron Paramagnetic Resonance (EPR) Studies of Photocatalytic Halogen Atom Transfer Intermediates Involving Organic Amines and Its Applications[J]. Chinese Journal of Organic Chemistry, 2025, 45(10): 3866-3872.

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

分享此文

图/表 5

Scheme 1. Photocatalyst amino-carbon-centered radical involved halogan atom transfer (XAT)

Figure 1. ESR study of the intermediates in photo-activation of iodocyclohexane via XAT under Ar

Scheme 2. Photo-induced singletoxygen promoted amino-carbon-centered radical involved halogan atom transfer (XAT)

Figure 2. ESR study of singletoxygen promoted light-induced activation of iodocyclohexane via XAT (A) 1-Methylquinoxalin-2(1H)-one (0.1 mol/L)＋nBu3N (0.2 mol/L)＋iodocyclohexane (0.1 mol/L)＋DMPO (0.1 mol/L) in DMSO. (B) Time resolved ESR study of the intermediates of 1-methylquinoxalin-2(1H)- one (0.1 mol/L)＋trybutylamine (0.2 mol/L)＋iodocyclohexane (0.1 mol/ L)＋DMPO (0.1 mol/L) in DMSO

Table 1. Photocatalytic alkylation of quinoxalin-2(1H)-one via XAT mechanism

参考文献 10

[1]	Tian, X.; Liu, Y.; Yakubov, S.; Schütte, J.; Chiba, S.; Barham, J. P. Chem. Soc. Rev. 2024, 53, 263.
[2]	(a) Kavita, K.; Das, P. K. J. Chem. Phys. 2002, 117, 2038.
	(b) Liu, W.; Li, J.; Huang, C.-Y.; Li, C.-J. Angew. Chem., Int. Ed. 2020, 59, 1786.
[3]	(a) Zidan, M.; McCallum, T.; Swann, R.; Barriault, L. Org. Lett. 2020, 22, 8401.
	(b) Deneny, P. J.; Kumar, R.; Gaunt, M. J. Chem. Sci. 2021, 12, 12812.
	(c) Jiang, Y.; Yin, Y.; Jiang, Z. Chin. J. Org. Chem. 2024, 44, 1733 (in Chinese).
	(蒋译锋, 尹艳丽, 江智勇, 有机化学, 2024, 44, 1733.) doi: 10.6023/cjoc202401035
[4]	(a) Juliá, F.; Constantin, T.; Leonori, D. Chem. Rev. 2022, 122, 2292.
	(b) Sachidanandan, K.; Niu, B.; Laulhé, S. ChemCatChem 2023,15, e202300860.
[5]	Yan, S.; Yu, W.; Zhang, J.; Fan, H.; Lu, Z.; Zhang, Z.; Wang, T. J. Org. Chem. 2022, 87, 1574.
[6]	(a) Buettner, C. S.; Schnürch, M.; Bica-Schröder, K. J. Org. Chem. 2022, 87, 11042.
	(b) Zhai, S.; Wang, R.; Dong, Q.; Cheng, J.; Zheng, M.; Wang, X. Org. Chem. Front. 2023, 10, 4816.
	(c) Hossain, M. M.; Shaikh, A. C.; Moutet, J.; Gianetti, T. L. Nat. Synth. 2022, 1, 147.
	(d) Zhang, T.; Huang, H. Angew. Chem., Int. Ed. 2023,62, e202310114.
	(e) Mao, B.; Zhang, X.-Y.; Wei, Y.; Shi, M. Chem. Commun. 2022, 58, 3653.
[7]	(a) Jiao, Y.; Shi, X.; Yu, S. Chem. Commun. 2023, 59, 13336.
	(b) Fan, Q.; Huang, J.; Lin, S.; Chen, Z.-H.; Li, Q.; Yin, B.; Wang, H. ACS Catal. 2024, 14, 299.
	(c) Wang, T.; Yu, W.; Lan, J.; Wang, H.; Jiang, Z.; Li, Y.; Fu, J. Chem. Catal. 2023, 3, 100619.
	(d) Huang, L.-Q.; Yang, D.-Y.; Dong, C.-L.; He, Y.-H.; Guan, Z. Adv.Synth. Catal. 2023, 365, 2553.
	(e) Wang, Z.; Li, X.; Li, W.; Cao, Y.; Li, H. Org. Chem. Front. 2023, 10, 4250.
	(f) Yedase, G. S.; Jha, A. K.; Yatham, V. R. J. Org. Chem. 2022, 87, 5442.
	(g) Wang, S.; Ren, D.; Liu, Z.; Yang, D.; Wang, P.; Gao, Y.; Qi, X.; Lei, A. Nat. Synth. 2023, 2, 1202.
[8]	(a) Buettner, G. R. Free Radical Biol. Med. 1987, 3, 259.
	(b) Zhou, Y.; Zhou, M.; Chen, M.; Su, J.; Du, J.; Song, Q. RSC Adv. 2015, 5, 103977.
	(c) Huang, C.; Ci, R.-N.; Qiao, J.; Wang, X.-Z.; Feng, K.; Chen, B.; Tung, C.-H.; Wu, L.-Z. Angew. Chem., Int. Ed. 2021, 60, 11779.
	(d) Li, J.; Zhang, Z.; Wu, L.; Zhang, W.; Chen, P.; Lin, Z.; Liu, G. Nature 2019, 574, 516.
	(e) Toybenshlak, M.; Carmieli, R. Isr. J. Chem. 2019, 59, 1020.
	(f) Liu, Y.; Shi, B., Liu, Z.; Gao, R.; Huang, C.; Alhumade, H.; Wang, S.; Qi, X.; Lei, A. J. Am. Chem. Soc. 2021, 143, 20863.
	(g) Liu, X.-H.; Yu, H.-Y.; Huang, J.-Y.; Zhou, X.-T.; Xue, C.; Ji, H.-B. Chem. Commun. 2023, 59, 243.
[9]	(a) Tian, M.; Liu, S.; Bu, X.; Yu, J.; Yang, X. Chem.-Eur. J. 2020, 26, 369.
	(b) Peng, S.; Hu, D.; Hu, J.-L.; Lin, Y.-W.; Tang, S.-S.; Tang, H.-S.; He, J.-Y.; Cao, Z.; He, W.-M. Adv. Synth. Catal. 2019, 361, 5721. doi: 10.1002/adsc.201901163
	(c) Xie, L.-Y.; Bai, Y.-S.; Xu, X.-Q.; Peng, X.; Tang, H.-S.; Huang, Y.; Lin, Y.-W.; Cao, Z.; He, W.-M. Green Chem. 2020, 22, 1720.
	(d) Ouyang, W.-T.; Jiang, J.; Jiang, Y.-F.; Li, T.; Liu, Y.-Y.; Ji, H.-T.; Ou, L.-J.; He, W.-M. Chin. Chem. Lett. 2024, 35, 110038.
	(e) Xu, Y.-D.; Xing, Y.-M.; Ji, H.-T.; Ou, L.-J.; He, W.-B.; Peng, J.; Wang, J.-S.; Jiang, J.; He, W.-M. J. Org. Chem. 2024, 89, 17701.
[10]	(a) Cao, S.; Chen, J.-X.; Zhang, X.-L.; Song, X.; Song, W.-Y.; Wu, Y.-S.; Zhang, Y.-H.; Liu, Z. Org. Lett. 2024, 26, 5833.
	(b) Zhao, W.; Zhang, Y.; Yuan, S.; Yu, X.; Liu, L.; Li, J. J. Org. Chem. 2023, 88, 6218.
	(c) Yuan, X.-Y.; Si, Y.-F.; Li, X.; Wu, S.-J.; Zeng, F.-L.; Lv, Q.-Y.; Yu, B. Org. Chem. Front. 2022, 9, 2728.
	(d) Zhang, M.; Nan, G.; Zhao, X.; Wei, W. Chin. J. Org. Chem. 2022, 42, 4315 (in Chinese).
	(张孟琪, 南光明, 赵晓辉, 魏伟, 有机化学, 2022, 42, 4315.) doi: 10.6023/cjoc202209013
	(e) Dong, J.; Xuan, L.; Wang, C.; Zhao, C.; Wang, H.; Yan, Q.; Wang, W.; Chen, F. Chin. J. Org. Chem. 2024, 44, 111 (in Chinese).
	(董江湖, 宣良明, 王池, 赵晨熙, 王海峰, 严琼姣, 汪伟, 陈芬儿, 有机化学, 2024, 44, 111.) doi: 10.6023/cjoc202307016
	(f) Chen, X.-M.; Song, L.; Pan, J.; Zeng, F.; Xie, Y.; Wei, W.; Yi, D. Chin. Chem. Lett. 2024, 35, 110112.
	(g) Feng, Q.; Hao, J.; Hu, Y.; Fu, R.; Wei, W.; Yi, D. Chin. Chem. Lett. 2025, 36, 110582.
	(h) Sun, J.; Yang, H.; Zhang, B. Green Chem. 2022, 24, 858.

[1]	祝辉, 吴鹏, 钟晨鸣, 李舒铭, 林钢, 刘雪粉, 罗书平. 供体-受体-供体(D-A-D)型芳香酮设计合成与光催化C(sp³)—H偶联反应性能研究[J]. 有机化学, 2025, 45(9): 3441-3449.
[2]	刘丽强, 南军, 段兴宇, 王昊龙, 蔡巷, 王梓诚, 张恩泽, 孙彦民. 三齿P配体钌络合物催化脂肪醇胺N-烷基化反应研究[J]. 有机化学, 2025, 45(8): 2983-2988.
[3]	解人杰, 谢复开, 孙然, 王欣, 王钰佳, 李蕾, 王贺. 电子供体-受体复合物(EDA)介导N-芳基丙烯酰胺与芳基硫鎓盐的自由基环化反应[J]. 有机化学, 2025, 45(8): 2913-2922.
[4]	史茜, 李忠玉, 李晗. 杂环金属铱配合物光敏剂的研究进展[J]. 有机化学, 2025, 45(7): 2389-2405.
[5]	高根伟, 李震, 李炎, 陆熹. 光/镍协同催化C(sp²)—C(sp³)键构建研究进展[J]. 有机化学, 2025, 45(6): 1905-1919.
[6]	谭永波, 舒洪波, 黄华文. 光诱导N-芳基丙烯酰胺参与的吲哚酮合成研究进展[J]. 有机化学, 2025, 45(6): 2086-2108.
[7]	周强, 杨宝臻, 郝贵林, 罗木鹏, 曹石, 赵蓓, 袁华, 王守国. 铑(III)催化的非活化烯烃与α-重氮羰基化合物的对映选择性烯丙位C—H键烷基化反应[J]. 有机化学, 2025, 45(6): 2109-2120.
[8]	李顺曦, 游力栩, 李玉龙, 舒伟. 光介导氨及其等价体参与的碳氮成键反应研究进展[J]. 有机化学, 2025, 45(5): 1460-1477.
[9]	黄嘉浩, 黄雅豪, 胡鹏. 氢原子转移介导的光催化C(sp³)—H键氧化反应进展[J]. 有机化学, 2025, 45(5): 1509-1522.
[10]	周思成, 刘运奎. P/N-杂配铜(I)光催化剂介导的可见光催化反应进展[J]. 有机化学, 2025, 45(5): 1644-1668.
[11]	陈雨佳, 刘志林, 陈凯, 向皞月, 阳华. 无金属、光催化氧化苄基C—H键以获得羰基官能团[J]. 有机化学, 2025, 45(5): 1755-1762.
[12]	林风, 张艳, 吴明, 刘会艳, 郝文娟, 姜波. 利用可见光引发1,6-烯炔的增环酰化双官能化制备1-茚酮衍生物[J]. 有机化学, 2025, 45(5): 1729-1738.
[13]	洪洋, 邓红平. 可见光催化的酸性C(sp³)—H键官能团化反应研究进展[J]. 有机化学, 2025, 45(5): 1569-1590.
[14]	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.
[15]	蒋晨阳, 尹艳丽, 江智勇. 光酶催化不对称自由基加成反应研究进展[J]. 有机化学, 2025, 45(5): 1614-1633.

光催化有机胺参与的卤原子转移中间体的电子自旋共振(EPR)研究及其应用

Electron Paramagnetic Resonance (EPR) Studies of Photocatalytic Halogen Atom Transfer Intermediates Involving Organic Amines and Its Applications

RichHTML

PDF

补充材料

可视化

摘要/Abstract

引用此文

分享此文

图/表 5

参考文献 10

相关文章 15

编辑推荐

相关统计

本文评价