Visible-Light-Mediated Radical Truce-Smiles Rearrangement via Arylazo Sulfones.

ABSTRACT: We present a photocatalyst-free, visible-light-mediated Truce-Smiles rearrangement (TSR) for the selective difunctionalization of olefins by exploiting photoactivatable arylazo sulfones as sulfonyl radical precursors. This method efficiently affords β-sulfonyl-α-arylpropamides in high yields with excellent stereoselectivity. Furthermore, by incorporating a readily available chiral amino acid auxiliary (α-tert-butyl-leucine), we successfully developed a stereoselective variant of the TSR reaction, delivering optically enriched α-arylpropamides with excellent diastereoselectivity (up to 20:1 dr). DFT calculations provided detailed insight into the key factors governing reactivity and selectivity, particularly the contrasting behaviors of N-alkyl and N-aryl acrylamides. O

SUBMITTER: Di Terlizzi L 

PROVIDER: S-EPMC12569698 | biostudies-literature | 2025 Oct

REPOSITORIES: biostudies-literature