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

doi:10.6023/cjoc202506016

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

Jiarui Liang, Jinlan Li, Yun Jiang, Qiuli Yao, Yingshu Xu, Anjun Wang. 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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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