Nickel-Catalyzed Reductive Carboxylation and Amidation Reactions

Area of Science:

• Organic Chemistry
• Catalysis
• Synthetic Methodology

Background:

• Carboxylic acids and amides are vital in pharmaceuticals, agrochemicals, and materials.
• Traditional synthesis methods for these functional groups are often limited.
• Developing novel catalytic protocols is crucial for efficient synthesis.

Purpose of the Study:

• To review advances in nickel-catalyzed reductive carboxylation and amidation.
• To highlight methodologies developed in the authors' laboratories.
• To provide insights into the reaction mechanisms for predictive power.

Main Methods:

• Utilizing nickel catalysts with carbon dioxide and isocyanates.
• Employing less reactive starting materials like organic halides, alcohols, and C-H bonds.
• Investigating chain-walking and [1,4]-Ni shift mechanisms for C-H functionalization.

Main Results:

• Successful formation of carboxylic acids and amides from diverse, less reactive precursors.
• Demonstrated control over site-selectivity in C-H functionalization reactions.
• Enabled synthesis of densely functionalized molecules and isotopically labeled compounds.

Conclusions:

• Nickel-catalyzed reductive carboxylation and amidation provide versatile alternatives to traditional methods.
• These reactions offer precise control over selectivity and access to complex molecules.
• Despite mechanistic challenges, these protocols show great promise for academic and industrial applications.