Overcoming Limitations in Decarboxylative Arylation via Ag-Ni Electrocatalysis

Area of Science:

• Organic Chemistry
• Catalysis
• Electrochemistry

Background:

• Decarboxylative cross-coupling (DCC) is a powerful synthetic tool.
• Previous DCC methods face limitations such as harsh conditions and expensive reagents.
• Redox-active esters (RAE) offer a versatile substrate class for DCC.

Purpose of the Study:

• To develop a practical and efficient protocol for decarboxylative cross-coupling of RAEs and halo(hetero)arenes.
• To overcome limitations of existing DCC methodologies.
• To establish a robust and scalable electrocatalytic system.

Main Methods:

• Development of a unique silver-nickel (Ag-Ni) electrocatalytic platform.
• Utilized redox-active esters (RAE) and halo(hetero)arenes as coupling partners.
• Employed a simple commercial potentiostat, air-stable conditions, and technical-grade solvents.

Main Results:

• Achieved efficient decarboxylative cross-coupling under mild, air-stable conditions at room temperature.
• Demonstrated the use of inexpensive ligands, nickel sources, and substoichiometric silver nitrate (AgNO3).
• Benchmarked results against state-of-the-art methods, confirming efficiency and practicality.

Conclusions:

• The developed Ag-Ni electrocatalytic system provides a simplified and robust approach to DCC.
• The protocol enables rapid access to challenging chemical structures and diverse molecular scaffolds.
• The method is adaptable to various scales, from milligram synthesis to decagram flow chemistry.