Electrochemical Ring-Opening Dicarboxylation of Strained Carbon–Carbon Single Bonds with CO₂: Facile Synthesis of Diacids and Derivatization into Polyesters

Abstract

Diacids are important monomers in the polymer industry to construct valuable materials. Dicarboxylation of unsaturated bonds, such as alkenes and alkynes, with CO2 has been demonstrated as a promising synthetic method. However, dicarboxylation of CC single bonds with CO2 has rarely been investigated. Herein we report a novel electrochemical ring-opening dicarboxylation of CC single bonds in strained rings with CO2. Structurally diverse glutaric acid and adipic acid derivatives were synthesized from substituted cyclopropanes and cyclobutanes in moderate to high yields. In contrast to oxidative ring openings, this is also the first realization of an electroreductive ring-opening reaction of strained rings, including commercialized ones. Control experiments suggested that radical anions and carbanions might be the key intermediates in this reaction. Moreover, this process features high step and atom economy, mild reaction conditions (1 atm, room temperature), good chemoselectivity and functional group tolerance, low electrolyte concentration, and easy derivatization of the products. Furthermore, we conducted polymerization of the corresponding diesters with diols to obtain a potential UV-shielding material with a self-healing function and a fluorine-containing polyester, whose performance tests showed promising applications.

Electrocarboxylation of Aryl Epoxides with CO2for the Facile and Selective Synthesis of β‐Hydroxy Acids

“…Importantly, treating ( R )‐styrene oxide with CO 2 under standard conditions gave the racemic carboxylation product 2 f (Scheme 4a), which further implicated the benzyl radical intermediate in this transformation. In accordance with our experimental results and literature reports, [13, 14] the mechanism was proposed for the electroreductive ring‐opening carboxylation of epoxides with CO 2 (Scheme 4b). Magnesium ions were continuously generated on the anode and bound with epoxides, providing intermediate I .…”

Efficient Synthesis of Diphenyl Carbonate from CO2, Phenol, and Carbon Tetrachloride under Mild Conditions

“…The possible reason is that a high pressure resulted in a low phenol concentration in the liquid phase because of the dilution by CO 2 dissolution, and such an effect of the CO 2 pressure on the catalytic activity was also reported for the synthesis of cyclic carbonate from epoxide and CO 2. − Thus, the optimal pressure was 0.20 MPa.…”

Recent Advances in Electrocarboxylation with CO2

“…Electrocarboxylation of cyclopropane derivatives 48 with CO 2 was reported by Yu and co‐workers (Scheme 15, d) [40] . The trans ‐1,2‐diphenylcyclopropane was chosen as the model substrate, and yield of electrocarboxylation was found strongly influenced by the current density and cathode materials, as Nb cathode and constant current of 15 mA could afford the good yield of 82%.…”