Electrochemically Driven Radical Alkylation of Alkenes with 1,3-Dicarbonyl Compounds

doi:10.6023/cjoc202601014

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (4): 1659-1667.DOI: 10.6023/cjoc202601014 Previous Articles Next Articles

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电化学驱动1,3-二羰基化合物与烯烃的自由基烷基化反应

刘勇^a, 李娟^a, 王凌凡^a, 黄宝彤^a, 彭凌子^b^,^*(), 宋琎^a^,^*(), 郭昌^b^,^*()

^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:2026-01-12 修回日期:2026-03-31 发布日期:2026-04-13
通讯作者: 彭凌子, 宋琎, 郭昌
基金资助:
国家自然科学基金(22471002); 安徽省自然科学基金(2308085Y12)

Electrochemically Driven Radical Alkylation of Alkenes with 1,3-Dicarbonyl Compounds

Yong Liu^a, Juan Li^a, Lingfan Wang^a, Baotong Huang^a, Lingzi Peng^b^,^*(), Jin Song^a^,^*(), Chang Guo^b^,^*()

^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:2026-01-12 Revised:2026-03-31 Published:2026-04-13
Contact: Lingzi Peng, Jin Song, Chang Guo
Supported by:
National Natural Science Foundation of China(22471002); Anhui Provincial Natural Science Foundation(2308085Y12)

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Abstract

Developing sustainable and efficient methods for the transformation of 1,3-dicarbonyl compounds and alkene functionalization represents a pivotal endeavor for advancing the frontiers of synthetic organic chemistry. Herein, an electrochemically driven functionalization reaction of 1,3-dicarbonyl compounds and alkenes is reported, which enables the efficient construction of α-alkylated 1,3-dicarbonyl compounds. This protocol avoids additional chemical oxidants/reductants, proceeds under mild and environmentally benign conditions, and exhibits excellent functional group tolerance, furnishing a diverse array of target products in moderate to good yields. Mechanistic studies indicate that electrochemically generated 1,3-dicarbonyl radicals add to alkenes, followed by single-electron transfer (SET) oxidation and nucleophilic alcohol quenching, thereby realizing efficient alkene functionalization.

Key words: electrochemistry, 1,3-dicarbonyl compounds, radical reaction, alkene functionalization

Cite this article

Yong Liu, Juan Li, Lingfan Wang, Baotong Huang, Lingzi Peng, Jin Song, Chang Guo. Electrochemically Driven Radical Alkylation of Alkenes with 1,3-Dicarbonyl Compounds[J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1659-1667.

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References 13

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Entry	Cp₂Fe/mol%	Electrolyte	Solvent	Yield^b/%
1	20	ⁿBu₄NBF₄	MeOH/TFE (4 mL/10 μL)	30
2	20	Et₄NPF₆	MeOH/TFE (4 mL/10 μL)	32
3	20	Et₄NBF₄	MeOH/TFE (4 mL/10 μL)	30
4	20	ⁿBu₄NPF₆	MeOH/TFE (4 mL/10 μL)	63
5	10	ⁿBu₄NPF₆	MeOH/TFE (4 mL/10 μL)	55
6	25	ⁿBu₄NPF₆	MeOH/TFE (4 mL/10 μL)	78
7	25	ⁿBu₄NPF₆	MeOH (4 mL)	43
8	25	ⁿBu₄NPF₆	DCE/MeOH (2 mL/2 mL)	26
9	25	ⁿBu₄NPF₆	Toluene/MeOH (2 mL/2 mL)	Trace
10	25	ⁿBu₄NPF₆	DCM/MeOH (2 mL/2 mL)	40
11	0	ⁿBu₄NPF₆	MeOH/TFE (4 mL/10 μL)	n.d.
12^c	25	ⁿBu₄NPF₆	MeOH/TFE (4 mL/10 μL)	n.d.
13^d	25	ⁿBu₄NPF₆	MeOH/TFE (4 mL/10 μL)	10

Entry	Cp₂Fe/mol%	Electrolyte	Solvent	Yield^b/%
1	20	ⁿBu₄NBF₄	MeOH/TFE (4 mL/10 μL)	30
2	20	Et₄NPF₆	MeOH/TFE (4 mL/10 μL)	32
3	20	Et₄NBF₄	MeOH/TFE (4 mL/10 μL)	30
4	20	ⁿBu₄NPF₆	MeOH/TFE (4 mL/10 μL)	63
5	10	ⁿBu₄NPF₆	MeOH/TFE (4 mL/10 μL)	55
6	25	ⁿBu₄NPF₆	MeOH/TFE (4 mL/10 μL)	78
7	25	ⁿBu₄NPF₆	MeOH (4 mL)	43
8	25	ⁿBu₄NPF₆	DCE/MeOH (2 mL/2 mL)	26
9	25	ⁿBu₄NPF₆	Toluene/MeOH (2 mL/2 mL)	Trace
10	25	ⁿBu₄NPF₆	DCM/MeOH (2 mL/2 mL)	40
11	0	ⁿBu₄NPF₆	MeOH/TFE (4 mL/10 μL)	n.d.
12^c	25	ⁿBu₄NPF₆	MeOH/TFE (4 mL/10 μL)	n.d.
13^d	25	ⁿBu₄NPF₆	MeOH/TFE (4 mL/10 μL)	10

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电化学驱动1,3-二羰基化合物与烯烃的自由基烷基化反应

Electrochemically Driven Radical Alkylation of Alkenes with 1,3-Dicarbonyl Compounds

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