Research on Selective Dehalogenation of α,α,α-Trihalogen (Chloro, Bromo) methyl Ketones Under Electrochemical Conditions
Received date: 2023-03-10
Online published: 2023-05-15
Supported by
Natural Science Foundation of Xinjiang Uygur Autonomous Region of China(2022D01A207); National Natural Science Foundation of China(22161046)
The regulation of reaction to efficient and highly selective transformation into distinct valuable molecules separately from the same materials is a remarkable fundamental process in organic synthesis. Selective halogenation and dehalogenation could greatly benefit as organohalogen compounds are versatile building blocks, key intermediates and pharmaceutically essential molecules. α,α-Dihalomethyl ketones have many unique biological and organic synthetic properties. They are valuable structural frameworks in natural products, pharmaceuticals, agrochemicals and organic synthesis. α,α-Dihalomethyl ketones are one of the most important intermediates in organic synthesis. Electrochemistry has become a powerful tool in organic synthesis to avoid the use of expensive and toxic oxidants or reductants to reduce the production of harmful and toxic by-products. Therefore, in this paper, the selective dehalogenation of α,α,α-trihalogen (chloro, bromo) methyl ketones under electrochemical conditions was studied, and 17 kinds of α,α-dibromomethyl ketones and 17 kinds of α,α-dichloromethyl ketones were prepared with the highest yield of 92%. The reaction has the advantages of mild conditions, simple operation and high tolerance of functional groups. The typical procedure is as follows: the electrolysis was carried out in an undivided electrolytic cell, with a platinum anode (10 mm×10 mm×0.2 mm), and a platinum cathode (10 mm×10 mm×0.2 mm). α,α,α-Trihalomethyl ketones (0.5 mmol, 1.0 equiv.) and electrolyte (n-Bu4NHSO4 or tetrabutylammonium fluoride, 0.25 mmol, 0.5 equiv.) were dissolved in 5 mL solvent (ClCH₂CH₂Cl or CH3CN). The reaction mixture was electrolyzed under a constant current of 10 mA and at room temperature until the complete consumption of starting material as monitored by TLC or NMR. After the reaction, EtOAc (10 mL×3) was added, and then washed with water (10 mL×3) and then with brine (10 mL). The organic fraction was dried and concentrated with anhydrous MgSO4. The residue was purified by silica gel chromatography to give the dehalogenated product.
Kanbinuer Nuermaimaiti , Chao Wang , Shiwei Luo , Abudu Rexit Abulikemu . Research on Selective Dehalogenation of α,α,α-Trihalogen (Chloro, Bromo) methyl Ketones Under Electrochemical Conditions[J]. Acta Chimica Sinica, 2023 , 81(6) : 582 -587 . DOI: 10.6023/A23030075
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