Coupling CO₂ Electroreduction to CO with alkyne Alkoxycarbonylation

Area of Science:

• Organic Chemistry
• Electrochemistry
• Sustainable Chemistry

Background:

• Alkynes are versatile building blocks in organic synthesis.
• Carbonylation reactions often require a reliable carbon monoxide (CO) source.
• Electrocatalytic reduction of carbon dioxide (CO₂) offers a sustainable pathway to valuable chemicals like CO.

Purpose of the Study:

• To develop an efficient and direct method for generating carbon monoxide (CO) from carbon dioxide (CO₂) electroreduction.
• To couple this CO generation with alkyne alkoxycarbonylation for the synthesis of α- or β-substituted acrylates.
• To establish a sustainable and integrated process for producing valuable acrylate derivatives.

Main Methods:

• Coupling alkyne alkoxycarbonylation with the electrocatalytic reduction of CO₂ to CO in a two-compartment system.
• Collecting the CO-enriched gaseous mixture produced from CO₂ electroreduction.
• Directly utilizing the collected CO gas in the subsequent alkoxycarbonylation reaction.

Main Results:

• Successful generation of a CO-enriched gaseous mixture from CO₂ electroreduction.
• Demonstrated direct use of the electrogenerated CO in alkyne alkoxycarbonylation.
• Identified CO content as critical, with optimal results achieved using gas mixtures containing >15 vol % CO.
• Achieved efficient synthesis of α- or β-substituted acrylates.

Conclusions:

• The integrated process provides an efficient and simple CO source derived from CO₂ electroreduction for alkoxycarbonylation.
• This method offers a sustainable alternative for producing substituted acrylates.
• The two-compartment system facilitates the direct utilization of electrogenerated CO, enhancing reaction efficiency.