Nickel-Catalyzed Aryl Group Interconversion: A Non-Equilibrium Strategy for Aryl Nitrile Synthesis
Hiroki Tanaka1, Eito Moriya1, Yuna Onozawa1
1Department of Applied Chemistry, Waseda University, 513 Wasedatsurumakicho, Shinjuku, Tokyo 162-0041, Japan.
JACS Au
|February 27, 2026
Summary
This study introduces a novel nickel-catalyzed reaction for aryl group interconversion, transforming aromatic esters into valuable nitriles. The process utilizes a unique decarbonylative step, avoiding excess reagents and enabling efficient synthesis.
Area of Science:
- Organic Chemistry
- Catalysis
- Synthetic Methodology
Background:
- Cross-electrophile coupling constructs C-C bonds using metal catalysis.
- Aryl group interconversion swaps aromatic groups between electrophiles via ligand exchange.
- Existing methods often require excess reagents due to reversibility.
Purpose of the Study:
- To develop a nickel-catalyzed aryl group interconversion method.
- To enable the transformation of aromatic esters into nitriles.
- To establish an irreversible pathway for efficient synthesis.
Main Methods:
- Nickel-catalyzed reaction between aromatic esters and 2-cyanopyridine.
- Utilizing a decarbonylative ether formation step to drive the reaction.
- Investigating the mechanism via oxidative addition and anionic ligand exchange.
Main Results:
- Efficient synthesis of pharmaceutically relevant nitriles from aromatic esters.
- Accommodates a wide range of aromatic ester substrates.
- The reaction proceeds via irreversible decarbonylative ether formation and anionic CN/OPh ligand exchange.
Conclusions:
- A novel, irreversible nickel-catalyzed aryl group interconversion is established.
- This method overcomes limitations of traditional reversible aryl group exchange reactions.
- The transformation provides a highly efficient route to valuable nitrile products.
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