Photoredox/Nickel-Catalyzed Single-Electron Tsuji–Trost Reaction: Development and Mechanistic Insights
Dr. Jennifer K. Matsui
Department of Chemistry, University of Pennsylvania, Roy and Diana Vagelos Laboratories, Philadelphia, PA, 19104-6323 USA
Search for more papers by this authorDr. Álvaro Gutiérrez-Bonet
Department of Chemistry, University of Pennsylvania, Roy and Diana Vagelos Laboratories, Philadelphia, PA, 19104-6323 USA
Search for more papers by this authorMadeline Rotella
Department of Chemistry and Biochemistry, University of Maryland, College Park, MD, 20742 USA
Search for more papers by this authorDr. Rauful Alam
Department of Chemistry, University of Pennsylvania, Roy and Diana Vagelos Laboratories, Philadelphia, PA, 19104-6323 USA
Search for more papers by this authorCorresponding Author
Prof. Osvaldo Gutierrez
Department of Chemistry and Biochemistry, University of Maryland, College Park, MD, 20742 USA
Search for more papers by this authorCorresponding Author
Prof. Gary A. Molander
Department of Chemistry, University of Pennsylvania, Roy and Diana Vagelos Laboratories, Philadelphia, PA, 19104-6323 USA
Search for more papers by this authorDr. Jennifer K. Matsui
Department of Chemistry, University of Pennsylvania, Roy and Diana Vagelos Laboratories, Philadelphia, PA, 19104-6323 USA
Search for more papers by this authorDr. Álvaro Gutiérrez-Bonet
Department of Chemistry, University of Pennsylvania, Roy and Diana Vagelos Laboratories, Philadelphia, PA, 19104-6323 USA
Search for more papers by this authorMadeline Rotella
Department of Chemistry and Biochemistry, University of Maryland, College Park, MD, 20742 USA
Search for more papers by this authorDr. Rauful Alam
Department of Chemistry, University of Pennsylvania, Roy and Diana Vagelos Laboratories, Philadelphia, PA, 19104-6323 USA
Search for more papers by this authorCorresponding Author
Prof. Osvaldo Gutierrez
Department of Chemistry and Biochemistry, University of Maryland, College Park, MD, 20742 USA
Search for more papers by this authorCorresponding Author
Prof. Gary A. Molander
Department of Chemistry, University of Pennsylvania, Roy and Diana Vagelos Laboratories, Philadelphia, PA, 19104-6323 USA
Search for more papers by this authorGraphical Abstract
Coming to light: Report herein is a highly regioselective, intermolecular, nickel-catalyzed photoredox allylic substitution that expands both the radical and electrophile scope of dual photoredox/Ni-catalyzed reactions. Quantum mechanical calculations shed light on the mechanistic pathway, supporting a Ni0 to NiII oxidative addition followed by an inner-sphere radical addition. PC=photocatalyst, RP=radical precursor.
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.
Supporting Information
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- 31For all of the calculations, dispersion-corrected, broken-spin (U)DFT functionals (UM06/6–311+G(d,p)-SMD(water)//UB3LYP/6-31G(d) and UB3LYP-D3/6–311+G(d,p)-SMD(water)//UB3LYP/6-31G(d)) were used. Further, the energy profile using dynamic correlation, open-shell domain-based local pair natural orbital coupled-cluster calculations (DLPNO-CCSD(T)/def2-TZVPP-SMD(water)//UB3LYP/6-31G(d)) were compared, which are known to provide accurate energies (within 3 kJ mol−1) with the computational cost comparable to DFT calculations. Overall, all methods provided similar conclusions (see the Supporting Information for further details). For simplicity, only UM06/6–311+G(d,p)-SMD(water)//UB3LYP/6-31G(d) energies will be discussed in the manuscript.
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- 33We also considered the protonation of B′′ followed by: 1) outer-sphere C(sp2)−C(sp3) bond formation and 2) radical addition, with subsequent inner-sphere C(sp2)−C(sp3) bond formation. However, the barriers for both protonated inner-sphere and outer-sphere pathways were higher in energy than the anionic pathway (see the Supporting Information).
