亚化学计量三氟甲烷磺酸酐/二甲基亚砜协同促进的三价磷到三级磷氧化物的氧化转化

doi:10.6023/cjoc202510024

有机化学 ›› 2026, Vol. 46 ›› Issue (3): 888-897.DOI: 10.6023/cjoc202510024 上一篇下一篇

研究论文

亚化学计量三氟甲烷磺酸酐/二甲基亚砜协同促进的三价磷到三级磷氧化物的氧化转化

李明, 王智超, 石大伟, 杨凤坤, 王长城, 杨斌^*()

烟台大学化学化工学院山东烟台 264005

收稿日期:2025-10-27 修回日期:2025-12-18 发布日期:2026-01-15
通讯作者: 杨斌
基金资助:
国家自然科学基金(22001225); 烟台市科技创新发展计划基础研究(2024JCYJ044)

Sub-stoichiometric Trifluoromethanesulfonic Anhydride/Dimethyl Sulfoxide-Mediated Cooxidation of Trivalent Phosphine to Tertiary Phosphine Oxides

Ming Li, Zhichao Wang, Dawei Shi, Fengkun Yang, Changcheng Wang, Bin Yang^*()

School of Chemistry and Chemical Engineering, Yantai University, Yantai, Shandong 264005

Received:2025-10-27 Revised:2025-12-18 Published:2026-01-15
Contact: Bin Yang
Supported by:
National Natural Science Foundation of China(22001225); Fundamental Research Projects of Science & Technology Innovation and Development Plan in Yantai City(2024JCYJ044)

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摘要/Abstract

开发了一种亚化学计量三氟甲烷磺酸酐(Tf₂O)和二甲基亚砜(DMSO)协同促进的三价磷试剂到三级磷氧化物的高效氧化反应. 该反应使用亚化学计量的Tf₂O和DMSO作为氧化剂, 反应条件温和, 反应速率快, 在不影响产率的情况下可进行有效的放大, 为三级磷氧化物的制备提供了一种高效、实用的方法. 该反应展现出良好的底物普适性, 多种三价磷试剂在该反应体系下都能良好地兼容. 在机理实验的基础上, 提出了该反应可能同时存在的两种反应路径.

关键词: 磷化学, 亚化学计量, 协同氧化, 三级磷氧化物

A sub-stoichiometric trifluoromethanesulfonic anhydride/dimethyl sulfoxide-mediated cooxidation approach has been developed for the efficient oxidation of phosphines to phosphine oxides. By avoiding the use of stoichiometric oxidants or toxic reagents, this procedure provides an economical and practical route to a variety of phosphine oxides. A broad range of P(III)-compounds are well compatible with this transformation. The mild conditions, short reaction time, and scale-up preparation enable the potential application of this method to the late-stage industrial production.

Key words: phosphorus chemistry, sub-stoichiometric, cooxidation, tertiary phosphine oxides

引用此文

李明, 王智超, 石大伟, 杨凤坤, 王长城, 杨斌. 亚化学计量三氟甲烷磺酸酐/二甲基亚砜协同促进的三价磷到三级磷氧化物的氧化转化[J]. 有机化学, 2026, 46(3): 888-897.

Ming Li, Zhichao Wang, Dawei Shi, Fengkun Yang, Changcheng Wang, Bin Yang. Sub-stoichiometric Trifluoromethanesulfonic Anhydride/Dimethyl Sulfoxide-Mediated Cooxidation of Trivalent Phosphine to Tertiary Phosphine Oxides[J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 888-897.

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参考文献 21

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Entry	Tf₂O/ equiv.	DMSO/ equiv.	Solvent	T/℃	t/h	Yield/%
1	0.5	—	DMAc	r.t.	12	40
2	0.5	—	1,4-Dioxane	r.t.	12	67
3	0.5	—	Toluene	r.t.	12	83
4	0.5	—	DCE	r.t.	12	80
5	0.5	—	MeCN	r.t.	12	81
6	0.5	—	Toluene	40	12	90
7	0.5	—	Toluene	60	12	81
8	0.5	—	Toluene	40	1	91
9	0.5	—	Toluene	40	0.5	93
10	0.5	—	Toluene	40	0.25	83
11	0.2	—	Toluene	40	0.5	34
12	0.5	1.0	Toluene	40	0.5	95
13	0.1	1.0	Toluene	40	0.5	35
14	0.2	0.6	Toluene	40	0.5	98
15	0.2	0.5	Toluene	40	0.5	87
16^b	0.2	0.6	Toluene	40	0.5	36
17^c	0.2	0.6	Toluene	40	0.5	67
18^d	0.2	0.6	Toluene	40	0.5	N.D
19	—	0.6	Toluene	40	0.5	N.R

Entry	Tf₂O/ equiv.	DMSO/ equiv.	Solvent	T/℃	t/h	Yield/%
1	0.5	—	DMAc	r.t.	12	40
2	0.5	—	1,4-Dioxane	r.t.	12	67
3	0.5	—	Toluene	r.t.	12	83
4	0.5	—	DCE	r.t.	12	80
5	0.5	—	MeCN	r.t.	12	81
6	0.5	—	Toluene	40	12	90
7	0.5	—	Toluene	60	12	81
8	0.5	—	Toluene	40	1	91
9	0.5	—	Toluene	40	0.5	93
10	0.5	—	Toluene	40	0.25	83
11	0.2	—	Toluene	40	0.5	34
12	0.5	1.0	Toluene	40	0.5	95
13	0.1	1.0	Toluene	40	0.5	35
14	0.2	0.6	Toluene	40	0.5	98
15	0.2	0.5	Toluene	40	0.5	87
16^b	0.2	0.6	Toluene	40	0.5	36
17^c	0.2	0.6	Toluene	40	0.5	67
18^d	0.2	0.6	Toluene	40	0.5	N.D
19	—	0.6	Toluene	40	0.5	N.R

亚化学计量三氟甲烷磺酸酐/二甲基亚砜协同促进的三价磷到三级磷氧化物的氧化转化

Sub-stoichiometric Trifluoromethanesulfonic Anhydride/Dimethyl Sulfoxide-Mediated Cooxidation of Trivalent Phosphine to Tertiary Phosphine Oxides

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