Electrochemical Radical Dienylation Reaction of Arylphosphine Oxides

doi:10.6023/cjoc202509004

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (3): 1050-1059.DOI: 10.6023/cjoc202509004 Previous Articles Next Articles

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电化学驱动芳基膦氧化物自由基二烯基化反应

王馨玉^a, 黄晨佩^a, 郭昌^b, 宋琎^a^,^*()

^a 安徽大学物质科学与信息技术研究院合肥 230601
^b 中国科学技术大学合肥微尺度物质科学国家研究中心合肥微尺度物质科学国家研究中心合肥 230026

收稿日期:2025-09-04 修回日期:2025-10-22 发布日期:2025-11-27
通讯作者: 宋琎
基金资助:
国家自然科学基金(22471002); 安徽省自然科学基金(2308085Y12); 安徽省大学生创新训练计划(S202510357568)

Electrochemical Radical Dienylation Reaction of Arylphosphine Oxides

Xinyu Wang^a, Chenpei Huang^a, Chang Guo^b, Jin Song^a^,^*()

^a Institutes of Physical Science and Information Technology, Anhui University, Hefei 230601
^b Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei 230026

Received:2025-09-04 Revised:2025-10-22 Published:2025-11-27
Contact: Jin Song
Supported by:
National Natural Science Foundation of China(22471002); Anhui Provincial Natural Science Foundation(2308085Y12); Anhui Provincial College Student Innovation Training Program(S202510357568)

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Abstract

The development of straightforward and environmentally friendly techniques for synthesizing organophosphorus compounds with C(sp²)—P bonds would be of great value for the advancement of synthetic chemistry. An electrochemically driven dienylation strategy of arylphosphine oxides with allenylsilanes is reported for the efficient synthesis of dienyl phosphorus compounds. A wide range of dienyl organophosphorus compounds with various functional group tolerance were facilely obtained in moderate to great yield. Mechanistic studies indicate that the desired C(sp²)—P bond is constructed through the radical addition process between the phosphoryl radical and the allene carbon.

Key words: electrochemical, dienylation, phosphoryl radical, C(sp²)—P bond

Cite this article

Xinyu Wang, Chenpei Huang, Chang Guo, Jin Song. Electrochemical Radical Dienylation Reaction of Arylphosphine Oxides[J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 1050-1059.

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Fig. & Tab. 6

References 12

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Entry	Base	Solvent	Yield^b/%
1	NEt₃	V(DCM)∶V(MeCN)=1∶2	36
2	NEt₃	V(DCE)∶V(MeCN)=1∶2	26
3	NEt₃	V(DCM)∶V(DCE)=1∶2	24
4	NEt₃	V(DCM)∶V(THF)=1∶2	21
5	ⁱPr₂NEt	V(DCM)∶V(MeCN)=1∶2	22
6	KO^tBu	V(DCM)∶V(MeCN)=1∶2	Trace
7	DMAP	V(DCM)∶V(MeCN)=1∶2	27
8	K₃PO₄	V(DCM)∶V(MeCN)=1∶2	43
9	NaOAc	V(DCM)∶V(MeCN)=1∶2	39
10	K₃PO₄	V(DCM)∶V(TFE)=1∶2	47
11	K₃PO₄	V(DCM)∶V(TFE)=1∶2	75
12	—	V(DCM)∶V(TFE)=1∶2	<5
13^c	K₃PO₄	V(DCM)∶V(TFE)=1∶2	N.d.
14^d	K₃PO₄	V(DCM)∶V(TFE)=1∶2	N.d.
15^e	K₃PO₄	V(DCM)∶V(TFE)=1∶2	44

Entry	Base	Solvent	Yield^b/%
1	NEt₃	V(DCM)∶V(MeCN)=1∶2	36
2	NEt₃	V(DCE)∶V(MeCN)=1∶2	26
3	NEt₃	V(DCM)∶V(DCE)=1∶2	24
4	NEt₃	V(DCM)∶V(THF)=1∶2	21
5	ⁱPr₂NEt	V(DCM)∶V(MeCN)=1∶2	22
6	KO^tBu	V(DCM)∶V(MeCN)=1∶2	Trace
7	DMAP	V(DCM)∶V(MeCN)=1∶2	27
8	K₃PO₄	V(DCM)∶V(MeCN)=1∶2	43
9	NaOAc	V(DCM)∶V(MeCN)=1∶2	39
10	K₃PO₄	V(DCM)∶V(TFE)=1∶2	47
11	K₃PO₄	V(DCM)∶V(TFE)=1∶2	75
12	—	V(DCM)∶V(TFE)=1∶2	<5
13^c	K₃PO₄	V(DCM)∶V(TFE)=1∶2	N.d.
14^d	K₃PO₄	V(DCM)∶V(TFE)=1∶2	N.d.
15^e	K₃PO₄	V(DCM)∶V(TFE)=1∶2	44

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电化学驱动芳基膦氧化物自由基二烯基化反应

Electrochemical Radical Dienylation Reaction of Arylphosphine Oxides

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