A Copper(I)-Catalyzed Sulfonylative Hiyama Cross-Coupling

Area of Science:

• Organic Chemistry
• Catalysis
• Sulfone Synthesis

Background:

• Diaryl sulfones are important structural motifs in pharmaceuticals and materials.
• Existing synthetic methods often require harsh conditions or lack functional group tolerance.

Purpose of the Study:

• To develop an air-tolerant catalytic method for synthesizing diaryl sulfones.
• To explore the scope and limitations of the new reaction.

Main Methods:

• Copper-catalyzed cross-coupling of aryl silanes with aryl iodides using DABSO as the sulfur dioxide source.
• Investigation of reaction mechanism using control experiments and Density Functional Theory (DFT) calculations.

Main Results:

• Successful synthesis of various diaryl sulfones under mild, air-tolerant conditions.
• Demonstrated tolerance of diverse polar functional groups including amines, ketones, esters, and aldehydes.
• Elucidation of a mechanism involving a key Cu(I)-sulfinate intermediate formed via SO2 insertion.

Conclusions:

• The developed Cu-catalyzed sulfonylative Hiyama cross-coupling provides an efficient and versatile route to diaryl sulfones.
• The reaction's air tolerance and functional group compatibility make it a valuable tool for organic synthesis.