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Photoredox/Nickel-Catalyzed Single-Electron Tsuji-Trost Reaction: Development and Mechanistic Insights.

ABSTRACT: A regioselective, nickel-catalyzed photoredox allylation of secondary, benzyl, and ?-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 Ni0 to NiII oxidative addition pathway followed by radical addition and inner-sphere allylation.

SUBMITTER: Matsui JK

PROVIDER: S-EPMC6526374 | biostudies-literature | 2018 Nov

REPOSITORIES: biostudies-literature

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Photoredox/Nickel-Catalyzed Single-Electron Tsuji-Trost Reaction: Development and Mechanistic Insights.

Matsui Jennifer K JK Gutiérrez-Bonet Álvaro Á Rotella Madeline M Alam Rauful R Gutierrez Osvaldo O Molander Gary A GA

Angewandte Chemie (International ed. in English) 20181107 48

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<sup>0</sup> to Ni<sup>II</sup> oxidative addition pathway followed by radical addition and inner-sphere allylation. ...[more]

PMID: 30307672

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