Photoredox/Nickel‐Catalyzed Single‐Electron Tsuji–Trost Reaction: Development and Mechanistic Insights. (7th November 2018)

• Record Type: Journal Article
• Authors: Matsui, Jennifer K.; Gutiérrez‐Bonet, Álvaro; Rotella, Madeline; Alam, Rauful; Gutierrez, Osvaldo; Molander, Gary A.
• Is Part Of: Angewandte Chemie. Volume 130:Number 48(2018)
• Page Start: 16073
• Page End: 16077
• Publication Date: 2018-11-07
• Subjects: Allylverbindungen -- Nickel -- Photochemie -- Reaktionsmechanismen -- Synthesemethoden; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201809919
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: A regioselective, nickel‐catalyzed photoredox allylation of secondary, benzyl, and α‐alkoxy radical precursors is disclosed. Through this manifold, a variety of linear allylic alcohols and allylated monosaccharides are accessible in high yields under mild reaction conditions. Quantum mechanical calculations [DFT and DLPNO‐CCSD(T)] support the mechanistic hypothesis of a Ni 0 to Ni II oxidative addition pathway followed by radical addition and inner‐sphere allylation.