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

doi:10.6023/cjoc202509032

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (4): 1776-1787.DOI: 10.6023/cjoc202509032 Previous Articles Next Articles

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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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Abstract

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

Cite this article

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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Fig. & Tab. 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

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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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Fig. & Tab. 9

References 17

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