Journal
GREEN CHEMISTRY
Volume 24, Issue 7, Pages 2859-2870Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d1gc04584a
Keywords
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Funding
- Program for Leading Talents, Department of Science and Technology of Yunnan Province [2017HA013]
- 111 project [D21027]
- Yunnan Fundamental Research Project [202001AT070148]
- post-doctoral foundation of Yunnan province [ynbh18020]
- Key Laboratory of Forest Biotechnology in Yunnan (Southwest Forestry University)
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A novel electrocatalytic process was developed to prepare alpha,alpha-gem-dihalide ketones in an environmentally friendly manner. The reaction exhibited high yields of about 80% under ambient conditions without inert gas protection. The study also discovered a special dimer condensation phenomenon.
A novel, environmentally friendly electrocatalytic process has been developed to prepare alpha,alpha-gem-dihalide (F, Cl, and Br) ketones from alpha-mono-halide ketones in an aqueous solution containing alkali halide salts. The gem-dihalides could have the same or different halogens on the same carbon, depending on the reactant and inorganic halide salt used. An electron-withdrawing group, such as carbonyl, located at the alpha-site of mono-halogenated carbon, was essential to the reaction. The electrosyntheses were performed under ambient conditions without inert gas protection and displayed yields of about 80%. This method avoided the classical haloform elimination reaction. However, when the aqueous solution contained NaOH, two alpha-mono-halide ketone molecules had a special dimer condensation. The reaction mechanisms were explored by conducting GC-MS, EPR, and CV with DFT calculations. These revealed that in situ generation of a halogen radical initiated electrocatalytic halogenation, while the dimer condensation involved a hydroxyl radical-mediated C1 fragment elimination.
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