Year: 2026
Type: article
Abstract: Despite their centrality in molecular design, stereodefined tri- and tetrasubstituted alkenes remain challenging to access, as most olefinations favor lower substitution and fail under sterically congested settings. Herein, we report the photoinduced cross-denitrative olefination of nitroalkanes to afford tri- and tetrasubstituted alkenes. Visible light excitation of in situ-generated nitronates promotes a photo-stitching event via denitrative cross-coupling of two nitroalkanes. The transformation tolerates a variety of functionalized nitroalkanes, including carbonyl- and heterocycle-containing substrates, complements metathesis and carbonyl olefination, and scales efficiently. Mechanistic studies support a photoinitiated and photopropagated nucleophilic-radical substitution and radical-chain elimination sequence in which nitronates function as photoreductants to generate radical-anion intermediates that undergo a subsequent photodriven β-elimination. These findings establish a previously inaccessible light-driven elimination process for radical-mediated olefination from readily available building blocks.
DOI: 10.1021/jacs.6c06460
Institution: New York University
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
OpenAlex ID: W7168927789