Advancing Sulfinyl Radical Chemistry: An Asymmetric Smiles Rearrangement with Chiral Sulfoxides

Area of Science:

• Organic Chemistry
• Asymmetric Synthesis
• Photocatalysis

Background:

• Chiral N-sulfinyl amides are effective for asymmetric radical-mediated Smiles rearrangements.
• These rearrangements offer excellent stereocontrol in aryl group translocation.

Purpose of the Study:

• To develop a photocatalytic multicomponent asymmetric sulfinyl-Smiles rearrangement using readily available chiral sulfoxides.
• To synthesize enantioenriched sulfur-containing molecules with retention of the sulfinyl group.

Main Methods:

• Utilized chiral sulfoxides, radical precursors, and alkylating reagents.
• Employed a photocatalytic approach to initiate a cascade process.
• The cascade involved radical addition, stereocontrolled aryl migration, and C-S bond formation.

Main Results:

• Achieved enantioenriched sulfur-containing molecules via asymmetric sulfinyl-Smiles rearrangement.
• The process demonstrated high stereocontrol and formed two new C-C bonds and one C-S bond.
• The reaction proceeded efficiently under mild conditions with retention of the sulfinyl group.

Conclusions:

• This novel method provides access to valuable enantioenriched sulfur scaffolds.
• The synthesized compounds are versatile intermediates for further derivatization.
• The approach offers a powerful tool for constructing complex sulfur-containing molecules.