Semiheterogeneous Dual Nickel/Photocatalytic (Thio)etherification Using Carbon Nitrides

Area of Science:

• Organic Chemistry
• Materials Science
• Photocatalysis

Background:

• Cross-coupling reactions are vital in organic synthesis.
• Developing sustainable and efficient catalytic systems remains a key challenge.
• Metal-free photocatalysis offers a greener alternative for chemical transformations.

Purpose of the Study:

• To develop a metal-free heterogeneous photocatalyst for cross-coupling reactions.
• To investigate the use of carbon nitride materials in combination with homogeneous nickel catalysts.
• To demonstrate the efficiency and scope of the developed catalytic system under mild conditions.

Main Methods:

• Utilizing a recyclable carbon nitride material as a heterogeneous semiconductor.
• Employing homogeneous nickel catalysts for light-mediated cross-coupling.
• Testing the system with various electron-poor aryl bromides and primary/secondary alcohols, as well as water.
• Exploring applications in intramolecular reactions and synthesis of active pharmaceutical ingredients.
• Evaluating the coupling of aryl iodides with thiols.

Main Results:

• Successful light-mediated cross-coupling of aryl bromides with alcohols and water under mild conditions.
• Demonstrated recyclability of the metal-free heterogeneous semiconductor.
• Broad substrate scope including electron-poor aryl bromides and diverse alcohols.
• Successful application in intramolecular reactions and synthesis of active pharmaceutical ingredients.
• Applicability for coupling aryl iodides with thiols was also shown.

Conclusions:

• The developed carbon nitride/nickel catalyst system provides an efficient and sustainable method for cross-coupling reactions.
• The metal-free, recyclable nature of the semiconductor highlights its potential for green chemistry applications.
• The protocol's versatility extends to complex syntheses, including pharmaceutical ingredient preparation.