Deacylative Thiolation by Redox-Neutral Aromatization-Driven C-C Fragmentation of Ketones

Area of Science:

• Organic Chemistry
• Synthetic Chemistry

Background:

• Introducing thioether groups is crucial for synthesizing various organic molecules.
• Existing methods for thioether introduction often require harsh conditions or toxic heavy metals.

Purpose of the Study:

• To develop a novel, efficient, and environmentally friendly method for deacylative thiolation.
• To enable site-specific introduction of thioether groups into unactivated aliphatic positions of methyl ketones.

Main Methods:

• Deacylative thiolation of diverse methyl ketones.
• Utilizing a redox-neutral and heavy-metal-free reaction pathway.
• Employing condensation, aromatization-driven C-C fragmentation, and radical coupling with thiosulfonates.

Main Results:

• Successful deacylative thiolation of a broad scope of methyl ketone substrates.
• Demonstrated excellent functional group tolerance, allowing for late-stage derivatization.
• Established a new synthetic route for thioether group installation with high site-specificity.

Conclusions:

• The developed method offers a valuable tool for organic synthesis.
• The reaction proceeds via a radical chain mechanism, as supported by experimental and computational studies.
• This approach provides a sustainable and versatile alternative for thioether synthesis.