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. 2018 Nov 26;57(48):15847-15851.
doi: 10.1002/anie.201809919. Epub 2018 Nov 7.

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

Jennifer K Matsui  1 , Álvaro Gutiérrez-Bonet  1 , Madeline Rotella  2 , Rauful Alam  1 , Osvaldo Gutierrez  2 , Gary A Molander  1
Affiliations

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

Jennifer K Matsui et al. Angew Chem Int Ed Engl. .

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 Ni0 to NiII oxidative addition pathway followed by radical addition and inner-sphere allylation.

Keywords: allylic compounds; nickel; photochemistry; reaction mechanisms; synthetic methods.

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Conflict of interest statement

Conflict of interest

The author declare no conflict of interest.

Figures

Figure 1
Figure 1
Competing Ni(0)/Ni(I)/Ni(III) (circles), Ni(0)/Ni(II)/Ni(III) (squares), Ni(0)/Ni(II) (squares-triangles), pathways leading to C(sp3)-C(sp3) bond formation.
Scheme 1.
Scheme 1.
Exploring radical-based Tsuji-Trost reactivity under photoredox conditions.
Scheme 2.
Scheme 2.
Observation of linear and branched mixtures.
See this image and copyright information in PMC

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