Base-Metal Catalysis - presented by Prof. Lingling Chu and Assoc. Prof. Ming Joo Koh and Prof. Zhan Lu and Assoc. Prof. Tatsuhiko Yoshino and Prof. Naohiko Yoshikai

Base-Metal Catalysis

Lingling Chu, Ming Joo Koh, Zhan Lu and Tatsuhiko Yoshino

Prof. Lingling ChuAssoc. Prof. Ming Joo KohAssoc. Prof. Tatsuhiko YoshinoProf. Zhan Lu
Slide at 20:07
New Strategy for Asymmetric Radical Couplings
Chelation strategy
Sensitization strategy
tetrahedral
excited state
photoexcitation
planar
rigid nickel complex
ground state
favored reductive elimination
Chelation effect:
Trapping radical with excited Ni(II) complex:
Facilitating stereoselective radical capture
Modulating the geometries of nickel complexes
Impeding the reversible Ni-C bond homolysis
Enhanced reactivity and diversed selectivity via EnT
Enhancing the rigidity of Ni(III) intermediate
Less-exploited stereoselective control at excited Ni
J. Am. Chem. Soc. 2020, 142, 9604.
ACS Catal 2022, 12, 9779
J. Am. Chem. Soc. 2020, 142, 20390
Chem 2022, 9, 154
J. Am. Chem. Soc. 2023, in revision
Angew Chem. Int. Ed. 2022, e202116725
J. Am. Chem. Soc. 2023, 145, 9876
Nat. Commun 2023, 55
Angew Chem. Int. Ed. 2023, e202305426
Angew. Chem. Int. Ed. 2021, 26511
Angew. Chem. Int. Ed. 2019, 177
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References
  • 1.
    H. Tu et al. (2020) Enantioselective Three-Component Fluoroalkylarylation of Unactivated Olefins through Nickel-Catalyzed Cross-Electrophile Coupling. Journal of the American Chemical Society
  • 2.
    F. Wang et al. (2022) Selective Three-Component Reductive Alkylalkenylation of Unbiased Alkenes via Carbonyl-Directed Nickel Catalysis. ACS Catalysis
  • 3.
    J. Am. Chem. Soc. 2023, in revision
  • 4.
    H. Li et al. (2022) Selective Fluoromethyl Couplings of Alkynes via Nickel Catalysis. Angewandte Chemie International Edition
  • 5.
    S. Pan et al. (2023) Nickel‐Catalyzed Markovnikov‐Selective Hydrodifluoromethylation of Alkynes Using BrCF2H. Angewandte Chemie International Edition
  • 6.
    L. Guo et al. (2020) General Method for Enantioselective Three-Component Carboarylation of Alkenes Enabled by Visible-Light Dual Photoredox/Nickel Catalysis. Journal of the American Chemical Society
  • 7.
    L. Huo et al. (2023) Site- and Stereoselective Synthesis of Alkenyl Chlorides by Dual Functionalization of Internal Alkynes via Photoredox/Nickel Catalysis. Journal of the American Chemical Society
  • 8.
    X. Zhao et al. (2021) Divergent Aminocarbonylations of Alkynes Enabled by Photoredox/Nickel Dual Catalysis. Angewandte Chemie International Edition
  • 9.
    F. Song et al. (2019) Visible‐Light‐Enabled Stereodivergent Synthesis of E‐ and Z‐Configured 1,4‐Dienes by Photoredox/Nickel Dual Catalysis. Angewandte Chemie International Edition
  • 10.
    T. Long et al. (2023) Ligand-controlled stereodivergent alkenylation of alkynes to access functionalized trans- and cis-1,3-dienes. Nature Communications
  • 11.
    X. Li et al. (2022) Three-component enantioselective alkenylation of organophosphonates via nickel metallaphotoredox catalysis. Chem
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Summary (AI generated)

The change in the gene of the Nickel complex could allow for a selective radical capture process. Four excitations would enhance activity and selectivity through single electron or energy transfers. Selective control is important in photo-excited states.

In 2016, our group was interested in multi-component cross couplings because they can efficiently build complex molecules using simple materials. We anticipated that radical species would bring distinct activities and selectivity to these reactions. However, progress in this area has been slow due to the presence of multiple types of radical species, making it challenging to use a single Transition Metal catalyst to control the selectivity.