Work

Remote 1,5-Difunctionalization of Alkenes via a Sulfinyl-Smiles Rearrangement and Vinylcyclopropane Ring-Opening Cascade

Year: 2026

Type: article

Abstract: The enantioselective remote difunctionalization of alkenes via radical pathways remains a major challenge due to limited stereocontrol in open-shell processes. We report a photoredox-catalyzed asymmetric remote 1,5-difunctionalization of alkenes that combines the strain-release ring opening of vinylcyclopropanes with a stereocontrolled sulfinyl-Smiles rearrangement. This multistep radical cascade bypasses kinetically disfavored hydrogen atom transfer pathways and enables precise site selectivity with excellent enantioselectivity. Both sulfur- and carbon-centered radicals are accommodated, providing efficient access to enantioenriched α-aryl γ,δ-unsaturated amides and derivatives thereof under mild conditions.

Source: JACS Au

DOI: 10.1021/jacsau.6c00241

Authors: Yawen Hu, Klorenta Nitaj, Cristina Nevado

Institution: University of Zurich

Language: English

Topic: Radical Photochemical Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: gold

Estimated APC paid: $3,500

Funders: National Science Foundation, Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung, China Scholarship Council