Citation: Yang Qi-Liang, Wang Xiang-Yang, Weng Xin-Jun, Yang Xiang, Xu Xue-Tao, Tong Xiaofeng, Fang Ping, Wu Xin-Yan, Mei Tian-Sheng. Palladium-Catalyzed ortho-Selective C-H Chlorination of Arenes Using Anodic Oxidation[J]. Acta Chimica Sinica, ;2019, 77(9): 866-873. doi: 10.6023/A19040135 shu

Palladium-Catalyzed ortho-Selective C-H Chlorination of Arenes Using Anodic Oxidation

Yang Qi-Liang ^a,b,† ,
Wang Xiang-Yang ^c,† ,
Weng Xin-Jun ^b ,
Yang Xiang ^b ,
Xu Xue-Tao ^c ,
Tong Xiaofeng ^a ,
Fang Ping ^b ,
Wu Xin-Yan ^a,, ,
Mei Tian-Sheng ^b,,

a.
School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237
b.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
c.
School of Biotechnology and Health Science, Wuyi University, Jiangmen 529020

Corresponding author: Wu Xin-Yan, xinyanwu@ecust.edu.cn Mei Tian-Sheng, mei7900@sioc.ac.cn
Received Date: 19 April 2019
Available Online: 8 September 2019
Fund Project: the National Natural Science Foundation of China 21772222the National Natural Science Foundation of China 21821002Project supported by the National Natural Science Foundation of China (Nos. 21772222 and 21821002) and the Department of Education of Guangdong Province (Nos. 2017KTSCX185, 2017KSYS010, 2016KCXTD005)the Department of Education of Guangdong Province 2016KCXTD005the Department of Education of Guangdong Province 2017KSYS010the Department of Education of Guangdong Province 2017KTSCX185

Figures(6)

Aryl halides are key building blocks in organic synthesis for the construction of valuable natural products, medicinal and agricultural chemicals via transition metal-catalyzed coupling or substitution reactions. Halogenation is one of the most fundamental and important reactions in organic synthesis. Electrochemical transition-metal-catalyzed C-H functionalization has emerged as a powerful tool for molecular synthesis with the prospect of avoiding the use of costly and toxic oxidants or reductants, thereby reducing the footprint of undesirable, toxic byproducts. The palladium-catalyzed electrochemical C-H chlorination of benzamide derivatives directed by PIP amine directing group under divided cells has been demonstrated, in which readily available inorganic halides salts serve as halogen sources. The reaction features a broad substrate scope, high functional group tolerance, and compatibility of thiophene substrates. This reaction could be conducted on a gram scale, which is important for future application. Additionally, the sequential bromination and chlorination of C(sp²)-H bond constructs highly functionalized aromatic carboxylic acid derivatives. The typical procedure is as follows:The electrolysis was carried out in an H-type divided cell (anion-exchange membrane), with a RVC anode (10 mm×10 mm×12 mm) and a platinum cathode (10 mm×10 mm×0.2 mm). The anodic chamber was charged with Pd(OAc)₂ (5.6 mg, 0.025 mmol, 10 mol%) and benzamide derivative (0.25 mmol, 1.0 equiv.) and dissolved in DMF (10 mL). LiCl (847.8 mg, 20.0 mmol) was added in the cathodic chamber and dissolved in water (10 mL). Then the reaction mixture was electrolyzed under a constant current of 5 mA at 90℃ until the complete consumption of the starting material as monitored by TLC or ¹H NMR. After the reaction, EtOAc (50 mL) was added to dilute the mixture and then washed with water (20 mL×3) and then with brine (20 mL). The organic fraction was dried over Na₂SO₄ and concentrated. The resulting residue was purified by silica gel flash chromatography to give the chlorination product.
- organic electrosynthesis,
- transition metal catalysis,
- C-H activation,
- anodic oxidation,
- chlorination
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