Copper(i)-catalyzed sulfonylative Suzuki-Miyaura cross-coupling

Area of Science:

• Organic Chemistry
• Catalysis
• Synthetic Methodology

Background:

• Suzuki-Miyaura cross-coupling is a cornerstone of modern organic synthesis.
• Direct incorporation of sulfur dioxide into cross-coupling reactions remains challenging.
• Development of novel catalytic systems for C-S bond formation is highly sought after.

Purpose of the Study:

• To develop a novel sulfonylative-Suzuki-Miyaura cross-coupling reaction.
• To establish a single-step synthesis of diaryl sulfones.
• To explore the utility of sulfur dioxide as a direct C1 building block in cross-coupling.

Main Methods:

• A simple copper(I) catalyst was employed.
• Aryl boronic acids, aryl iodides, and DABSO (a sulfur dioxide surrogate) were used as starting materials.
• Reaction conditions were optimized for high yield and selectivity.

Main Results:

• A high-yielding, single-step synthesis of diaryl sulfones was achieved.
• This represents the first sulfonylative variant of the Suzuki-Miyaura reaction.
• Interruption of the reaction pathway led to the isolation of a copper-sulfinate intermediate, enabling access to diverse sulfone derivatives.

Conclusions:

• The developed copper-catalyzed reaction provides an efficient route to diaryl sulfones.
• The methodology allows for the synthesis of various sulfone compounds, including arylalkyl sulfones, β-hydroxyl sulfones, sulfonamides, and sulfonyl fluorides.
• This work expands the scope of cross-coupling reactions and sulfur dioxide utilization in synthesis.