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

doi:10.6023/cjoc202502030

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (10): 3866-3872.DOI: 10.6023/cjoc202502030 Previous Articles Next Articles

ARTICLES

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)

1. .pdf(6285KB)

Abstract

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

Cite this article

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.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 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

References 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]	Liqiang Liu, Jun Nan, Xingyu Duan, Haolong Wang, Xiang Cai, Zicheng Wang, Enze Zhang, Yanmin Sun. N-Alkylation of Aliphatic Alcohol Amine Catalyzed by Tridentate P Ligand Ruthenium Complex [J]. Chinese Journal of Organic Chemistry, 2025, 45(8): 2983-2988.
[2]	Renjie Xie, Fukai Xie, Ran Sun, Xin Wang, Yujia Wang, Lei Li, He Wang. Electron Donor-Acceptor (EDA) Complexes Mediated Free Radicals Cyclization of N-Arylacrylamide with Arylthionium Salts [J]. Chinese Journal of Organic Chemistry, 2025, 45(8): 2913-2922.
[3]	Qiang Zhou, Baozhen Yang, Guilin Hao, Mupeng Luo, Shi Cao, Bei Zhao, Hua Yuan, Shouguo Wang. Rhodium(III)-Catalyzed Enantioselective Allylic C—H Alkylation of Unactivated Alkenes with α‑Diazocarbonyl Compounds [J]. Chinese Journal of Organic Chemistry, 2025, 45(6): 2109-2120.
[4]	Sicheng Zhou, Yunkui Liu. Recent Progresses in P/N-Heteroleptic Cu(I)-Photocatalyst-Mediated Visible-Light-Driven Photocatalytic Reactions [J]. Chinese Journal of Organic Chemistry, 2025, 45(5): 1644-1668.
[5]	Lingwei Wu, Hao Cui, Xiao Zhang. Recent Advances in Water-Soluble Photocatalysts-Mediated Aqueous Reactions [J]. Chinese Journal of Organic Chemistry, 2025, 45(4): 1097-1118.
[6]	Guoen Wen, Shuo Gu, Haibing He, Shuanhu Gao. Synthetic Study of Kuroshine Alkaloids [J]. Chinese Journal of Organic Chemistry, 2025, 45(3): 977-987.
[7]	Yufei Xia, Li Jiang, Qiao Yang, Xiu Yu, Fengkun Chen. Triple Aza[6]helicenes with Circularly Polarized Luminescence: N-Alkylation as a Tool to Tune the Chiroptical Properties [J]. Chinese Journal of Organic Chemistry, 2024, 44(9): 2841-2846.
[8]	Jianling Hu, Chao Zhang, Wenda Zhu, Yepu He, Shuling Peng, Zhenqiang Chen, Mingyue Li, Zhiju Liu, Heru Chen. Design, Synthesis, and Preliminary Anti-tumor Activity Studies of Novel 1,2-Disubstituted Hydrazines [J]. Chinese Journal of Organic Chemistry, 2024, 44(6): 1870-1883.
[9]	Junjun Liu, Taotao Lu, Ping Ma, Qingyang Zhao, Fuk Yee Kwong. Palladium-Catalyzed C(sp³)—Si Bonds Transformation for Construct-ing Trifluoropropyl (Hetero)arenes through C(sp³)—C(sp²) Cross-Coupling Reactions [J]. Chinese Journal of Organic Chemistry, 2024, 44(4): 1319-1326.
[10]	Yuying Liu, Zhanwei Fu, Chao Yang, Mupeng Luo, Shurong Ban, Shouguo Wang. Rh(III)-Catalyzed Aminoalkylation of Alkenes with Diazo Compounds toward Functionalized Isoindolinones [J]. Chinese Journal of Organic Chemistry, 2024, 44(11): 3505-3517.
[11]	Jinshao Liang, Lihong Ruan, Xurong Shi, Yinzhi Chen, Chuhuang Song, Jun'an Xiao, Zhiping Liu. Mechanochemistry Enabled Friedel-Crafts Alkylation Reactions of Donor-Acceptor Cyclopropanes with 2-Indolymethanols [J]. Chinese Journal of Organic Chemistry, 2024, 44(11): 3437-3445.
[12]	Jing Hou, Yan Huang, Hao Li, Yuancui Wan, Yu Shao, Lewu Zhan, Dinghai Wang, Bindong Li. Recent Advances in the Application of Carbon Dioxide Radical Anion [J]. Chinese Journal of Organic Chemistry, 2024, 44(10): 3117-3135.
[13]	Jianghu Dong, Liangming Xuan, Chi Wang, Chenxi Zhao, Haifeng Wang, Qiongjiao Yan, Wei Wang, Fen'er Chen. Recent Advances in Visible-Light-Induced C(3)—H Functionalization of Quinoxalinones under Transition-Metal-Free or Photocatalyst-Free [J]. Chinese Journal of Organic Chemistry, 2024, 44(1): 111-136.
[14]	Chun-Xia Cheng, Lu-Ping Wu, Feng Sha, Xin-Yan Wu. Enantioselective Vinylogous Allylic Alkylation of Coumarins with Morita-Baylis-Hillman Carbonates Catalyzed by Chiral Phosphine-Amide [J]. Chinese Journal of Organic Chemistry, 2023, 43(9): 3188-3195.
[15]	Boyu Yan, Jieliang Wu, Jinfei Deng, Dan Chen, Xiushen Ye, Qiuli Yao. Recent Progress in Light-Driven Direct Dehydroxylation and Derivation of Alcohols [J]. Chinese Journal of Organic Chemistry, 2023, 43(9): 3055-3066.

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

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 5

References 10

Related Articles 15

Recommended Articles

Metrics

Comments