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

doi:10.6023/cjoc202510024

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (3): 888-897.DOI: 10.6023/cjoc202510024 Previous Articles Next Articles

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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
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: *E-mail: yangbin_hy@ytu.edu.cn
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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Abstract

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

Cite this article

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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Fig. & Tab. 6

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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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