可见光诱导的磷酰化环化合成磷酰基取代的吲哚并二氮䓬

doi:10.6023/cjoc202509032

有机化学 ›› 2026, Vol. 46 ›› Issue (4): 1776-1787.DOI: 10.6023/cjoc202509032 上一篇下一篇

研究论文

可见光诱导的磷酰化环化合成磷酰基取代的吲哚并二氮䓬

侯馨怡^a, 史同同^b, 李泽江^a^,^*(), 董庆昊^b, 孙凯^b^,^*(), 王薪^b^,^*()

^a 河北大学化学与材料科学学院河北保定 071002
^b 烟台大学药学院山东烟台 264005

收稿日期:2025-09-25 修回日期:2025-10-20 发布日期:2025-11-12
通讯作者: 李泽江, 孙凯, 王薪
基金资助:
国家自然科学基金(22301259); 山东省自然科学基金(ZR2023MB135); 山东省自然科学基金(ZR2024QB086)

Visible-Light-Induced Phosphorylation Cyclization to Phosphorylated Indole-Fused Diazepines

Xinyi Hou^a, Tongtong Shi^b, Zejiang Li^a^,^*(), Qinghao Dong^b, Kai Sun^b^,^*(), Xin Wang^b^,^*()

^a College of Chemistry and Materials Science, Hebei University, Baoding, Hebei 071002
^b School of Pharmacy, Yantai University, Yantai, Shandong 264005

Received:2025-09-25 Revised:2025-10-20 Published:2025-11-12
Contact: Zejiang Li, Kai Sun, Xin Wang
Supported by:
National Natural Science Foundation of China(22301259); Shandong Provincial Natural Science Foundation(ZR2023MB135); Shandong Provincial Natural Science Foundation(ZR2024QB086)

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摘要/Abstract

在室温下, 本工作发展了一种新颖的可见光诱导的磷酰化环化合成磷酰基取代的吲哚并二氮䓬. 该策略具有底物适用范围广、官能团兼容性良好、可规模化制备等优势; 同时, 通过硝化、氯化和氰基化等衍生化反应证明了该方案的实用性. 通过自由基抑制实验、开关光照射实验、荧光量子产率(AQE)计算、紫外-可见吸收光谱研究和循环伏安实验, 提出了能量转移介导的磷中心自由基反应途径.

关键词: 光催化, 自由基环化, 磷酰化, 氮杂中环

A novel visible-light induced phosphorylation cyclization to indole-fused medium-sized diazepines was estab- lished under room temperature. Broad substrate scope, good functional group compatibility, large-scale synthesis and derivatization via nitration, chlorination and cyanation demonstrate the utility of this protocol. P-centered radical involed energy transfer (EnT) process was proposed based on radical inhibition experiments, visible-light irradiation on-off test, apparent quantum efficiency (AQE) calculation, UV-vis absorption spectroscopic studies and cyclic voltammetry experiments.

Key words: photocatalysis, radical cyclization, phosphorylation, medium-sized N-heterocycles

引用此文

侯馨怡, 史同同, 李泽江, 董庆昊, 孙凯, 王薪. 可见光诱导的磷酰化环化合成磷酰基取代的吲哚并二氮䓬[J]. 有机化学, 2026, 46(4): 1776-1787.

Xinyi Hou, Tongtong Shi, Zejiang Li, Qinghao Dong, Kai Sun, Xin Wang. Visible-Light-Induced Phosphorylation Cyclization to Phosphorylated Indole-Fused Diazepines[J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1776-1787.

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图/表 9

Figure 1. Selected biologically active compounds containing indole units

Scheme 1. Synthesis of phosphorylated heterocycles via P-centered radicals routes

Entry	PC	Solvent	Oxidant	Yield^b/%
1	Eosin Y	MeCN	TBHP	21
2	Ru(bpy)₃Cl₂•6H₂O	MeCN	TBHP	39
3	Ir(ppy)₃	MeCN	TBHP	75
4	4-CzIPN	MeCN	TBHP	84
5	4-CzIPN	DCM	TBHP	40
6	4-CzIPN	EtOAc	TBHP	65
7	4-CzIPN	THF	TBHP	63
8	4-CzIPN	DMSO	TBHP	69
9	4-CzIPN	MeOH	TBHP	58
10	4-CzIPN	MeCN	O₂	0
11	4-CzIPN	MeCN	K₂S₂O₈	52
12	4-CzIPN	MeCN	BPO	43
13	—	MeCN	TBHP	0
14	4-CzIPN	MeCN	—	Trace

Table 1. Optimization of reaction conditionsa

Scheme 2. Substrate scope of 1 Reaction conditions: 1 (0.5 mmol), 2a (0.75 mmol), MeCN (5 mL), radiated under 30 W LED (450~460 nm) chimney under air at r.t. for 10 h, isolated yield.

Scheme 3. Substrate scope of 2 Reaction conditions: 1 (0.5 mmol), 2 (0.75 mmol), MeCN (5 mL), radiated under 30 W LED (450~460 nm) chimney under air at r.t. for 10 h, isolated yield.

Scheme 4. Gram-scale synthesis and derivatization study

Scheme 5. Reactions for mechanistic determination

Figure 2. (a) Fluorescence quenching studies; (b) Visible-light irradiation on-off experiments; (c) Cyclic voltammetry studies

Scheme 6. Favored mechanism to indole-fused diazepinones

参考文献 17

[1]	Li, J. L.; Zhao, Q.; Gou, C.; Li, Q. Z.; Leng, H. J.; Huang, Q. W.; Liu, Y. Adv. Synth. Catal. 2021, 363, 4497.
[2]	(a) Mizoguchi, H.; Oikawa, H.; Oguri, H. Nat. Chem. 2014, 6, 57.
	(b) Purgatorio, R.; Candia, M.; Catto, M.; Carrieri, A.; Pisani, L.; Palma, A. De.; Toma, M.; Ivanova, O. A.; Voskressensky, L. G.; Altomare, C. D. Eur. J. Med. Chem. 2019, 177, 414.
[3]	Faust, R.; Garratt, P. J.; Jones, R.; Yeh, L. K.; Tsotinis, A.; Panoussopoulou, M.; Calogeropoulou, T.; The, M. T.; Sugden, D. J. Med. Chem. 2000, 43, 1050.
[4]	(a) Disney, A. J. M.; Kellam, B.; Dekker, L. V. ChemMedChem 2016, 11, 972.
	(b) Gayler, K. M.; Kong, K.; Reisenauer, K.; Taube, J. H.; Wood, J. L. ACS Med. Chem. Lett. 2020, 11, 2441.
[5]	(a) Ohno, H.; Hamaguchi, H.; Ohata, M.; Tanaka, T. Angew. Chem., Int. Ed. 2003, 42, 1749.
	(b) Shiina, I. Chem. Rev. 2007, 107, 239.
[6]	(a) Lian, G.; Li, J.; Liu, P.; Sun, P. J. Org. Chem. 2019, 84, 9322.
	(b) Liu, Y. W.; Wang, M. M.; Zhang, Y. Q.; Xu, H.; Dai, H. X. Org. Lett. 2023, 25, 5406.
	(c) Chiu, W. J.; Chu, T. Y.; Barve, I. J.; Sun, C. M. Org. Lett. 2023, 25, 6246.
	(d) Guo, L.; Zhang, Z.; Zhang, F.; Sun, K.; Yu, B. Org. Lett. 2024, 26, 10982.
	(e) Li, J.; Ni, H.; Zhang, W.; Lai, Z.; Jin, H.; Zeng, L.; Cui, S. Chem. Sci. 2024, 15, 5211.
[7]	(a) Hua, H. L.; Zhang, B. S.; He, Y. T.; Qiu, Y. F.; Hu, J. Y.; Yang, Y. C.; Liang, Y. M. Chem. Commun. 2016, 52, 10396.
	(b) Zhao, L.; Yan, Z. H.; Tang, S.; Wei, Z. L.; Liao, W. W. Org. Lett. 2020, 23, 166.
	(c) Huang, X.; Shi, Y.; Wang, Y.; Jiao, J.; Tang, Y.; Li, J.; Xu, S.; Li, Y. Org. Lett. 2021, 23, 8365.
	(d) Qiu, Z. W.; Li, B. Q.; Liu, H. F.; Zhu, Z. Q.; Pan, H. P.; Feng, N.; Ma, A. J.; Peng, J. B.; Zhang, X. Z. J. Org. Chem. 2021, 86, 7490.
	(e) Jin, H. S.; Fang, Q. Y.; Wang, J. Q.; Zhao, L. M. Chem. Eur. J. 2023, 29, e202300467.
	(f) Chen, L. Q.; Zhu, C. F.; Zhang, S.; Liu, B. Y.; Tu, S. J.; Hao, W. J.; Jiang, B. Chin. Chem. Lett. 2023, 34, 108398.
	(g) Zhang, J. Y.; Chen, J. Y.; Gao, C. H.; Yu, L.; Ni, S. F.; Tan, W.; Shi, F. Angew. Chem., Int. Ed. 2023, 62, e202305450.
[8]	(a) Harada, S.; Yanagawa, M.; Nemoto, T. ACS Catal. 2020, 10, 11971.
	(b) Chen, C.; Zuo, X.; Tu, D.; Wan, B.; Zhang, Y. Org. Lett. 2020, 22, 4985.
	(c) Yang, S.; An, X. D.; Qiu, B.; Liu, R. B.; Xiao, J. Org. Lett. 2021, 23, 9100.
	(d) Antropov, S. M.; Tokmacheva, S. A.; Levina, I. I.; Ivanova, O. A.; Trushkov, I. V. Adv. Synth. Catal. 2024, 366, 2784.
[9]	Rapelli, C.; Sridhar, B.; Reddy, B. V. S. Org. Biomol. Chem. 2020, 18, 6710.
[10]	(a) Staveness, D.; Bosque, I.; Stephenson, C. R. Acc. Chem. Res. 2016, 49, 2295.
	(b) Woźniak, Ł.; Magagnano, G.; Melchiorre, P. Angew. Chem., Int. Ed. 2018, 57, 1068.
	(c) Staveness, D.; Collins III, J. L.; McAtee, R. C. Stephenson, C. R. Angew. Chem., Int. Ed. 2019, 58, 19000.
	(d) Latrache, M.; Hoffmann, N. Chem. Soc. Rev. 2021, 50, 7418.
	(e) Lu, M.-J.; Liang, R.-B.; Zhu, C.-M.; Tong, Q.-X.; Zhong, J.-J. Chin. J. Chem. 2023, 41, 1823.
	(f) Liang, R.-B.; Miao, T.-T.; Li, X.-R.; Huang, J.-B.; Ni, S.-F.; Li, S.-L.; Tong, Q.-X.; Zhong, J.-J. Chem. Sci. 2025, 16, 3580.
	(g) Zhang, R.-J.; Li, X.-R. Liang, R.-B.; Xiao, Y.-H.; Tong, Q.-X.; Zhong, J.-J.; Wu, L.-Z. Org. Lett. 2024, 26, 591.
[11]	(a) Wille, U. Chem. Rev. 2013, 113, 813.
	(b) Zhang, B.; Studer, A. Chem. Soc. Rev. 2015, 44, 3505.
	(c) Chen, Z. M.; Zhang, X. M.; Tu, Y. Q. Chem. Soc. Rev. 2015, 44, 5220.
	(d) Stuyver, T.; Chen, B.; Zeng, T.; Geerlings, P.; Proft, F. D.; Hoffmann, R. Chem. Rev. 2019, 119, 11291.
	(e) Wu, X.; Ma, Z.; Feng, T.; Zhu, C. Chem. Soc. Rev. 2021, 50, 11577.
	(f) Coppola, G. A.; Pillitteri, S.; Van der Eycken, E. V.; You, S. L.; Sharma, U. K. Chem. Soc. Rev. 2022, 51, 2313.
[12]	(a) Baumgartner, T.; Réau, R. Chem. Rev. 2006, 106, 4681.
	(b) De Clercq, E. Med. Res. Rev. 2011, 31, 118.
	(c) Queffélec, C.; Petit, M.; Janvier, P.; Knight, D. A.; Bujoli, B. Chem. Rev. 2012, 112, 3777.
[13]	(a) Cai, B. G.; Xuan, J.; Xiao, W. J. Sci. Bull. 2019, 64, 337.
	(b) Zeng, F. L.; Jia, Z.; Loh, T. P. Adv. Synth. Catal. 2024, 366, 4536.
[14]	(a) Zhang, Z.; Tan, P.; Wang, S.; Wang, H.; Xie, L.; Chen, Y.; Han, L.; Yang, S.; Sun, K. Org. Lett. 2023, 25, 4208.
	(b) Zhang, Z.; Fang, X.; Aili, A.; Wang, S.; Tang, J.; Lin, W.; Xie, L.; Chen, J.; Sun, K. Org. Lett. 2023, 25, 4598.
	(c) Sun, K.; Zhao, D.; Li, Q.; Ni, S.; Zheng, G. Zhang, Q. Sci. China Chem. 2023, 66, 2309.
	(d) Yin, Y.-F.; Liu, F.; Tian, M.; Han, L.-L.; Li, M.-H.; Tao, J.-F.; Liu, Q.; Sun, L.-L.; Xu, X.-M.; Sun, K. J. Org. Chem. 2025, 90, 7070.
[15]	Zhao, D.Y.; Wang, X.; Huang, J.-B.; Yu, T.-T.; Hao, E.-J.; Ni, S.-F.; Sun, K. Org. Lett. 2025, 27, 1030.
[16]	(a) Luo, J.; Zhang, J. ACS Catal. 2016, 6, 873.
	(b) Shang, T. Y.; Lu, L. H.; Cao, Z.; Liu, Y.; He, W. M.; Yu, B. Chem. Commun. 2019, 55, 5408.
[17]	(a) Zeng, F. L.; Zhang, Z. Y.; Yin, P. C.; Cheng, F. K.; Chen, X. L.; Qu, L. B.; Cao, Z. Y.; Yu, B. Org. Lett. 2022, 24, 7912.
	(b) Lu, Y. H.; Wu, C.; Hou, J. C.; Wu, Z. L.; Zhou, M. H.; Huang, X. J.; He, W. M. ACS Catal. 2023, 13, 13071.
	(c) Huang, Q.; Liu, J.; Wan, J. P Org. Lett. 2024, 26, 5263.
	(d) Zhou, Y.; Yang, W. H.; Dai, N. N.; Feng, J. Y.; Yang, M. Q.; Gao, W.; Li, Q. Deng, C. Lu, Z. Wei, W. T. Org. Lett. 2024, 26, 5074.
	(e) Lv, Y.; Ding, H.; You, J.; Wei, W.; Yi, D. Chin. Chem. Lett. 2024, 35, 109107.

可见光诱导的磷酰化环化合成磷酰基取代的吲哚并二氮䓬

Visible-Light-Induced Phosphorylation Cyclization to Phosphorylated Indole-Fused Diazepines

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