Visible-Light-Catalyzed Deoxyphosphonylation and Deoxyphosphinylation of Alkyl Alcohols via Thianthrenium Salts

doi:10.6023/cjoc202505005

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (12): 4468-4480.DOI: 10.6023/cjoc202505005 Previous Articles Next Articles

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可见光催化烷基醇经噻蒽盐的脱羟基(次)膦酰化反应

张欢^a^,^†, 崔中赫^a^,^†, 朱林^b^,^c^,^*(), 李超忠^a^,^b^,^c

^a 上海科技大学物质科学与技术学院上海 201210
^b 中国科学院上海有机化学研究所先进氮氟材料全国重点实验室先进氮氟材料全国重点实验室上海 200032
^c 南京大学化学化工学院配位化学全国重点实验室配位化学全国重点实验室南京 210093

收稿日期:2025-05-06 修回日期:2025-05-21 发布日期:2025-06-06
通讯作者: 朱林
作者简介:
^† 共同第一作者
基金资助:
南京大学化学化工学院配位化学全国重点实验室开放基金和国家自然科学基金(22193012); 南京大学化学化工学院配位化学全国重点实验室开放基金和国家自然科学基金(22193014); 南京大学化学化工学院配位化学全国重点实验室开放基金和国家自然科学基金(21971253)

Visible-Light-Catalyzed Deoxyphosphonylation and Deoxyphosphinylation of Alkyl Alcohols via Thianthrenium Salts

Huan Zhang^a, Zhonghe Cui^a, Lin Zhu^b^,^c^,^*(), Chaozhong Li^a^,^b^,^c

^a School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210
^b Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
^c State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093

Received:2025-05-06 Revised:2025-05-21 Published:2025-06-06
Contact: Lin Zhu
About author:
†These authors contributed equally to this work
Supported by:
Open Research Fund of State Key Laboratory of Coordination Chemistry, School of Chemistry and Engineering, Nanjing University, and the National Natural Science Foundation of China(22193012); Open Research Fund of State Key Laboratory of Coordination Chemistry, School of Chemistry and Engineering, Nanjing University, and the National Natural Science Foundation of China(22193014); Open Research Fund of State Key Laboratory of Coordination Chemistry, School of Chemistry and Engineering, Nanjing University, and the National Natural Science Foundation of China(21971253)

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Abstract

A photoredox-catalyzed system has been developed for the deoxyphosphonylation and deoxyphosphinylation of alkyl alcohols via thianthrenium salts. This methodology features simple reaction conditions, avoids the use of expensive reagents, and enables efficient recovery and reuse of thianthrenium reagent as hydroxyl-activating agent. Notably, both transformations exhibit broad substrate scope and good functional group compatibility, and have been successfully applied to the late-stage modification of various complex bioactive molecules. This protocol represents a promising methodology for practical synthesis of alkylphosphonates and alkylphosphinates.

Key words: alkanol, thianthrenium salt, deoxyphosphonylation, deoxyphosphinylation, radical

Cite this article

Huan Zhang, Zhonghe Cui, Lin Zhu, Chaozhong Li. Visible-Light-Catalyzed Deoxyphosphonylation and Deoxyphosphinylation of Alkyl Alcohols via Thianthrenium Salts[J]. Chinese Journal of Organic Chemistry, 2025, 45(12): 4468-4480.

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References 27

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Entry	Variation from optimal conditions	Yield^b/%
1	Without Et₃N	39
2	DMA as solvent, without Et₃N	24
3	MeCN as solvent, without Et₃N	Trace
4	DCE as solvent, without Et₃N	N.D.^c
5	EtOAc as solvent, without Et₃N	N.D.
6	DABCO instead of Et₃N	N.D.
7	Quinuclidine instead of Et₃N	10
8	DIPEA instead of Et₃N	61
9	None	81 (74^d)
10	1.0 equiv. Et₃N	59
11	3.0 equiv. Et₃N	82
12	4CzIPN instead of 4DPAIPN	73
13	fac-Ir(ppy)₃instead of 4DPAIPN	25
14	3DPA2FBN instead of 4DPAIPN	33
15	P-2 instead of P-1	35
16	P(OMe)₃ instead of P-1	25^e
17	1.0 equiv. P-1	65
18	3.0 equiv. P-1	83
19	390~410 nm blue LEDs	53
20	Without photocatalyst	N.D.
21	In the dark	N.D.

Entry	Variation from optimal conditions	Yield^b/%
1	Without Et₃N	39
2	DMA as solvent, without Et₃N	24
3	MeCN as solvent, without Et₃N	Trace
4	DCE as solvent, without Et₃N	N.D.^c
5	EtOAc as solvent, without Et₃N	N.D.
6	DABCO instead of Et₃N	N.D.
7	Quinuclidine instead of Et₃N	10
8	DIPEA instead of Et₃N	61
9	None	81 (74^d)
10	1.0 equiv. Et₃N	59
11	3.0 equiv. Et₃N	82
12	4CzIPN instead of 4DPAIPN	73
13	fac-Ir(ppy)₃instead of 4DPAIPN	25
14	3DPA2FBN instead of 4DPAIPN	33
15	P-2 instead of P-1	35
16	P(OMe)₃ instead of P-1	25^e
17	1.0 equiv. P-1	65
18	3.0 equiv. P-1	83
19	390~410 nm blue LEDs	53
20	Without photocatalyst	N.D.
21	In the dark	N.D.

可见光催化烷基醇经噻蒽盐的脱羟基(次)膦酰化反应

Visible-Light-Catalyzed Deoxyphosphonylation and Deoxyphosphinylation of Alkyl Alcohols via Thianthrenium Salts

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