Direct Electrochemical Defluorinative Carboxylation of gem-Difluoroalkenes with Carbon Dioxide
Shi-Liang Xie, Xiao-Tong Gao, Hai-Hong Wu
1State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Shanghai 200032, China.
Abstract:
We report a facile and economical synthesis of α-fluoroacrylic acids via direct electrochemical defluorinative carboxylation of gem-difluoroalkenes with CO2. By using a platinum plate as the working cathode and a cheap nickel plate as the anode in a user-friendly undivided cell under constant current conditions, the reactions proceed smoothly under room temperature, without the use of expensive transition metal catalysts, ligands, external base or reductant, affording the desired adducts in up to 83% yield and 20:1 Z/E ratio, with good functional group tolerance. A cyclic voltammetry study was conducted and suggested a novel ECEC process.
Related Concept Videos
Preparation of Carboxylic Acids: Carboxylation of Grignard Reagents
Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene
Carboxylic Acids to Methylesters: Alkylation using Diazomethane
Loss of Carboxy Group as CO2: Decarboxylation of β-Ketoacids
Electrophilic Aromatic Substitution: Friedel–Crafts Acylation of Benzene
Aldehydes and Ketones with Water: Hydrate Formation
The formation of hydrates is a reversible reaction. Hydrate formation is influenced by steric and electronic factors accompanying the alkyl substituents on the carbonyl group: The rate of hydrate formation increases with a decrease in the number of alkyl groups attached to the carbonyl carbon. Hence,...


