Electrochemical Synthesis of α-Fluoroalkylated Ketones using Sodium Fluoroalkylsulfinate

doi:10.6023/A23080386

Acta Chimica Sinica ›› 2024, Vol. 82 ›› Issue (2): 110-114.DOI: 10.6023/A23080386 Previous Articles Next Articles

Special Issue: 有机氟化学合集

Communication

氟烷基亚磺酸钠盐电化学合成α-氟烷基酮

李珊^a^,^b, 路俊欣^a, 刘杰^a, 蒋绿齐^a^,^*(), 易文斌^a^,^*()

a 南京理工大学化学与化工学院南京 210094
b 沙洲职业工学院张家港 215600

投稿日期:2023-08-20 发布日期:2023-10-23
基金资助:
国家自然科学基金(22078161); 国家自然科学基金(22108124); 中央高校基本科研业务费专项资金(30918011314); 中央高校基本科研业务费专项资金(30922010403); 江苏省青蓝工程(苏教师函(2022)29号); 六大高峰人才

Electrochemical Synthesis of α-Fluoroalkylated Ketones using Sodium Fluoroalkylsulfinate

Shan Li^a^,^b, Junxin Lu^a, Jie Liu^a, Lvqi Jiang^a(), Wenbin Yi^a()

a School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094
b Shazhou Professional Institute of Technology, Zhangjiagang 215600

Received:2023-08-20 Published:2023-10-23
Contact: * E-mail: lvqi.jiang@njust.edu.cn;yiwb@njust.edu.cn
Supported by:
National Natural Science Foundation of China(22078161); National Natural Science Foundation of China(22108124); Fundamental Research Funds for the Central Universities(30918011314); Fundamental Research Funds for the Central Universities(30922010403); Qing Lan Project (No. (2022)29); Six Talent Peaks Project in Jiangsu Province

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Abstract

The fluorine-containing group has a significant effect on properties such as lipophilicity, permeability, and metabolic stability of compounds. Therefore, the efficient introduction of fluorine-containing groups into pharmaceutical and agrochemical compounds, as well as functional organic materials, has become an important research field of chemistry. Undoubtedly, new methodologies for the efficient and highly selective incorporation of fluorinated substituents into diverse molecular structures continue to be in strong demand. During the past few years, electrosynthesis has been considered to be a practical and environmentally friendly synthetic tool. The application of electrochemical anodic oxidation in synthetic organic chemistry has drawn increasing attention. Electrochemistry utilizes direct interaction of electrons from the anode and cathode with the nucleus, avoids using strong oxidants, and minimizes byproduct formation. Herein we describe an electrochemical synthesis of α-trifluoromethylated ketones from alkenes based on sodium trifluoromethanesulfinate. Sodium trifluoromethanesulfinate generates trifluoromethyl radicals through anodic oxidation to attack the carbon-carbon double bonds of alkenes, and then oxidized in air atmosphere to obtain the target compounds. The optimized reaction conditions of electrochemical synthesis of α-trifluoromethylated ketones are as follows: 1 equiv. of alkenes, 2 equiv. of sodium trifluoromethanesulfinate, a mixture of CH₃CN/H₂O (V∶V=2∶1) as the solvent, 2 equiv. of lithium perchlorate as electrolyte, CF₃COOH as the sacrificial oxidant, graphite as the anode and platinum as the cathode, react at room temperature for 6 h under a constant current of 20 mA and air atmosphere, giving the corresponding α-trifluoromethyl-substituted ketones in 66%~84% yields. The reaction substrate has good applicability, and the reaction conditions are mild. Compared with the traditional methods, the electrocatalytic process avoids the use of peroxidants or expensive photocatalysts. In addition, this reaction can be applied to the synthesis of α-difluoromethylated ketones when using sodium difluoromethanesulfinate instead of sodium trifluoromethanesulfinate.

Key words: electrocatalysis, free radical, sodium trifluoromethanesulfinate, trifluoromethylated ketone

Cite this article

Shan Li, Junxin Lu, Jie Liu, Lvqi Jiang, Wenbin Yi. Electrochemical Synthesis of α-Fluoroalkylated Ketones using Sodium Fluoroalkylsulfinate[J]. Acta Chimica Sinica, 2024, 82(2): 110-114.

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Fig. & Tab. 5

References 19

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Entry	Variation of standard conditions	Yield^b/%
1	None	89
2	1.0 equiv. of CF₃SO₂Na	80
3	3.0 equiv. of CF₃SO₂Na	78
4	MeCN instead of MeCN/H₂O (V∶V=2∶1)	42
5	DCM instead of MeCN/H₂O (V∶V=2∶1)	23
6	MeCN/H₂O (V∶V=1∶1)	63
7	MeCN/H₂O (V∶V=4∶1)	71
8	nBu₄NClO₄instead of LiClO₄	79
9	nBu₄NPF₆instead of LiClO₄	75
10	nBu₄NBF₄ instead of LiClO₄	68
11	CH₃COOH instead of TFA	77
12	C(+)/Ni(–) instead of C(+)/Pt(–)	Trace
13	C(+)/C(–) instead of C(+)/Pt(–)	16
14	Pt(+)/Pt (–) instead of C(+)/Pt(–)	18
15	15 mA instead of 20 mA	81
16	25 mA instead of 20 mA	74

Entry	Variation of standard conditions	Yield^b/%
1	None	89
2	1.0 equiv. of CF₃SO₂Na	80
3	3.0 equiv. of CF₃SO₂Na	78
4	MeCN instead of MeCN/H₂O (V∶V=2∶1)	42
5	DCM instead of MeCN/H₂O (V∶V=2∶1)	23
6	MeCN/H₂O (V∶V=1∶1)	63
7	MeCN/H₂O (V∶V=4∶1)	71
8	nBu₄NClO₄instead of LiClO₄	79
9	nBu₄NPF₆instead of LiClO₄	75
10	nBu₄NBF₄ instead of LiClO₄	68
11	CH₃COOH instead of TFA	77
12	C(+)/Ni(–) instead of C(+)/Pt(–)	Trace
13	C(+)/C(–) instead of C(+)/Pt(–)	16
14	Pt(+)/Pt (–) instead of C(+)/Pt(–)	18
15	15 mA instead of 20 mA	81
16	25 mA instead of 20 mA	74

氟烷基亚磺酸钠盐电化学合成α-氟烷基酮

Electrochemical Synthesis of α-Fluoroalkylated Ketones using Sodium Fluoroalkylsulfinate

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