电化学驱动芳基膦氧化物自由基二烯基化反应

doi:10.6023/cjoc202509004

摘要/Abstract

开发简便、环境友好的C(sp²)—P键有机膦化合物合成技术对推动合成化学发展具有重要意义. 报道了一种电化学驱动的芳基膦氧化物与丙二烯硅的二烯基化策略, 可实现二烯基膦氧化物的高效合成. 该反应具有优异的官能团兼容性, 能够以中等至优良的收率便捷制备多种二烯基有机膦化合物. 机理研究表明, 目标C(sp²)—P键的形成是通过磷酰自由基与联烯的自由基加成过程实现.

关键词: 电化学, 二烯基化, 磷酰自由基, C(sp²)—P键

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

引用此文

王馨玉, 黄晨佩, 郭昌, 宋琎. 电化学驱动芳基膦氧化物自由基二烯基化反应[J]. 有机化学, 2026, 46(3): 1050-1059.

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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参考文献 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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