Visible-Light-Driven Halogen-Bond-Induced Direct Coupling of Diethyl α-Iodomethylphosphonates with Coumarins/Quinolinones

doi:10.6023/cjoc202506016

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (1): 135-145.DOI: 10.6023/cjoc202506016 Previous Articles Next Articles

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可见光驱动下卤键诱导的α-碘甲基膦酸二乙酯与香豆素/喹啉酮的直接偶联反应

梁家瑞, 李金兰, 蒋云, 姚秋丽, 徐应淑^*(), 王安俊^*()

遵义医科大学药学院贵州省化学药物创制全省重点实验室贵州遵义 563000

收稿日期:2025-06-11 修回日期:2025-08-13 发布日期:2025-09-17
通讯作者: 徐应淑, 王安俊
基金资助:
遵义市科技计划(遵市科合HZ 字(2023)169); 贵州省科技计划(黔科平台人才[2021]1350-005); 贵州省科学技术厅(黔科合平台人才- CXTD[2022]012)

Visible-Light-Driven Halogen-Bond-Induced Direct Coupling of Diethyl α-Iodomethylphosphonates with Coumarins/Quinolinones

Liang Jiarui, Li Jinlan, Jiang Yun, Yao Qiuli, Xu Yingshu^*(), Wang Anjun^*()

Guizhou Provincial Key Laboratory of Innovation and Manufacturing for Pharmaceuticals, School of Pharmacy, Zunyi Medical University, Zunyi, Guizhou 563000

Received:2025-06-11 Revised:2025-08-13 Published:2025-09-17
Contact: Xu Yingshu, Wang Anjun
Supported by:
Zunyi City Science and Technology Plan(Zun City Kehe HZ character [2023]169); Guizhou Province Science and Technology Plan(Guizhou Science Platform Talent [2021]1350-005); Science and Technology Department of Guizhou Province(QKHPTRC-CXTD2022-012)

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Abstract

α-Aryl phosphonates represent an important class of organophosphorus compounds with significant application value in medicinal chemistry. Meanwhile, coumarin and quinolinone are ubiquitous scaffold structures in this field. However, synthetic methods for α-phosphonylated coumarin/quinolinone derivatives remain limited. To address this, a visible-light- driven, halogen-bond-induced direct coupling reaction was developed, enabling the efficient covalent linkage between diethyl α-iodomethylphosphonate and coumarin or quinolinone. This transformation features mild reaction conditions, simple operation, excellent substrate compatibility, and high regioselectivity.

Key words: visible light, halogen bond, diethyl α-iodomethylphosphonates, coumarin/quinolone, direct coupling reaction

Cite this article

Liang Jiarui, Li Jinlan, Jiang Yun, Yao Qiuli, Xu Yingshu, Wang Anjun. Visible-Light-Driven Halogen-Bond-Induced Direct Coupling of Diethyl α-Iodomethylphosphonates with Coumarins/Quinolinones[J]. Chinese Journal of Organic Chemistry, 2026, 46(1): 135-145.

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References 17

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Entry	Electron donor	LED light/nm	1a∶2a	Solvent	Yield/%
1	DMAP	410~415	1∶4	MeCN	39
2	DMAP	410~415	1∶4	DMF	48
3	DMAP	410~415	1∶4	THF	—
4	DMAP	410~415	1∶4	DCM	Trace
5	DMAP	410~415	1∶4	MeOH	Trace
6	DMAP	410~415	1∶4	DMSO	71
7	Et₃N	410~415	1∶4	DMSO	17
8	DBU	410~415	1∶4	DMSO	16
9	PhOH	410~415	1∶4	DMSO	—
10	HE	410~415	1∶4	DMSO	—
11	PPh₃	410~415	1∶4	DMSO	Trace
12	DMAP	410~415	1∶2	DMSO	36
13	DMAP	410~415	1∶6	DMSO	72
14	DMAP	390~395	1∶4	DMSO	38
15	DMAP	440~445	1∶4	DMSO	47
16	—	410~415	1∶4	DMSO	—
17	DMAP	Dark	1∶4	DMSO	—

Entry	Electron donor	LED light/nm	1a∶2a	Solvent	Yield/%
1	DMAP	410~415	1∶4	MeCN	39
2	DMAP	410~415	1∶4	DMF	48
3	DMAP	410~415	1∶4	THF	—
4	DMAP	410~415	1∶4	DCM	Trace
5	DMAP	410~415	1∶4	MeOH	Trace
6	DMAP	410~415	1∶4	DMSO	71
7	Et₃N	410~415	1∶4	DMSO	17
8	DBU	410~415	1∶4	DMSO	16
9	PhOH	410~415	1∶4	DMSO	—
10	HE	410~415	1∶4	DMSO	—
11	PPh₃	410~415	1∶4	DMSO	Trace
12	DMAP	410~415	1∶2	DMSO	36
13	DMAP	410~415	1∶6	DMSO	72
14	DMAP	390~395	1∶4	DMSO	38
15	DMAP	440~445	1∶4	DMSO	47
16	—	410~415	1∶4	DMSO	—
17	DMAP	Dark	1∶4	DMSO	—

可见光驱动下卤键诱导的α-碘甲基膦酸二乙酯与香豆素/喹啉酮的直接偶联反应

Visible-Light-Driven Halogen-Bond-Induced Direct Coupling of Diethyl α-Iodomethylphosphonates with Coumarins/Quinolinones

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