Recent Advances in Electrochemical Carboxylation with CO₂

Area of Science:

• Organic Chemistry
• Electrochemistry
• Sustainable Chemistry

Background:

• Carbon dioxide (CO2) is a greenhouse gas but also a valuable C1 building block for chemical synthesis.
• Electrochemical synthesis offers a green approach for CO2 utilization by using electrons as reagents.
• Challenges remain in CO2 activation, selectivity control, and developing diverse electrolysis methods.

Purpose of the Study:

• To highlight contributions to selective electrochemical carboxylation of CO2 over the past seven years.
• To present new reaction systems, selectivity control methods, and activation strategies for CO2 utilization.
• To demonstrate the potential of organic electrosynthesis for sustainable chemical production.

Main Methods:

• Developed Ni-catalyzed electrochemical carboxylation of aryl halides and alkyl bromides.
• Established deep electroreductive systems for carboxylation of alkyl chlorides and PVC.
• Achieved dicarboxylation via C-C bond cleavage and dicarboxylative cyclization of dienes.
• Realized asymmetric nickel-catalyzed enantioselective electroreductive carboxylation.
• Developed new electrolysis modes for regiodivergent C-H carboxylation of N-heteroarenes.

Main Results:

• Demonstrated sustainable carboxylation without sacrificial anodes.
• Enabled direct modification and upgrading of waste polymers like PVC.
• Successfully achieved dicarboxylation and dicarboxylative cyclization reactions.
• Synthesized enantioenriched propargylic carboxylic acids via asymmetric carboxylation.
• Showcased reactor-dependent regiodivergent C-H carboxylation of N-heteroarenes.

Conclusions:

• Electrochemical carboxylation is a powerful and versatile tool for sustainable CO2 utilization.
• Significant progress has been made in activating inert substrates and controlling reaction selectivity.
• Further research in electrolysis modes and activation strategies will expand CO2 applications.