Room Temperature Anhydrous Suzuki-Miyaura Polymerization Enabled by C-S Bond Activation

Area of Science:

• Organic Chemistry
• Polymer Chemistry
• Materials Science

Background:

• Suzuki-Miyaura cross-coupling is vital for C-C bond formation.
• Protodeboronation of arylboronic acids limits precise conjugated polymer synthesis.
• Developing efficient and green polymerization methods is crucial.

Purpose of the Study:

• To develop an anhydrous, room temperature Suzuki-Miyaura cross-coupling reaction.
• To overcome protodeboronation issues in conjugated polymer synthesis.
• To provide a greener and more efficient protocol for alternating conjugated polymers.

Main Methods:

• Anhydrous room temperature Suzuki-Miyaura cross-coupling using (hetero)aryl boronic esters and aryl sulfides.
• Mechanistic studies involving the capture of a four-coordinated borate intermediate.
• Synthesis and characterization of thirty small molecules and twelve conjugated polymers.

Main Results:

• Demonstrated the universality of the reaction across various substrates.
• Identified direct transmetalation of boronic esters, suppressing protodeboronation.
• Achieved reduced homocoupling defects and enhanced optoelectronic properties in conjugated polymers.
• Successfully synthesized alternating conjugated polymers using a green protocol.

Conclusions:

• The developed anhydrous, room temperature Suzuki-Miyaura coupling is a versatile method for C-C bond formation.
• This protocol effectively prevents protodeboronation, leading to improved conjugated polymer synthesis.
• The reaction offers a sustainable and efficient approach for creating advanced optoelectronic materials.