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 17:18
Stereoselective Control of Radicals Stereoselective control of radicals: "Holy grail" of enantioselectivity Unpaired electron: notorious & difficult to control Low barrier for pyramidal inversion: racemization stereocontrol? Rapid diffusion controlled radical recombination unpaired electron chiral motifs Limited asymmetric strategies and reaction types established asymmetric radical-mediated additions asymmetric radical-mediated cross-couplings Lewis Acid catalysis Organocatalysis transition metal catalysis 58.693 Me Me Me Me M = Cu, Ni, Co, Cr, Fe, etc. Nickel (Ar)3d4s2 early transition state Transition Metals chiral ligand development new strategies in high demand Sibi, M. P.* et. al. Sibi, M. P.*. Bertrand, M. P.*, Nechab, M.* Reisman, S. E.* et. al. Chem. Rev. 2003, 103, 3263 Chem. Rev. 2022, 122, 5842 Chem. Rev. 2015, 115, 9587
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References
  • 1.
    M. P. Sibi et al. (2003) Enantioselective Radical Processes. Chemical Reviews
  • 2.
    S. Mondal et al. (2022) Enantioselective Radical Reactions Using Chiral Catalysts. Chemical Reviews
  • 3.
    A. H. Cherney et al. (2015) Enantioselective and Enantiospecific Transition-Metal-Catalyzed Cross-Coupling Reactions of Organometallic Reagents To Construct C–C Bonds. Chemical Reviews
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Summary (AI generated)

The generally proposed reaction pathway for metal-catalyzed couplings involves a key step where an LP radical is captured by a car and a N two complex to form the next three species. The N three species is then expected to undergo Reduction elimination to deliver the C Products. However, the process is complicated by the fact that the N three species is prone to undergoing a reversible nick carbon bond homolysis to regenerate the LG radical anemic two species. This reversible process makes the expected stereoselective radical capture process inefficient. As a result, the entire transformation of these radical couplings relies on the final Reduction to delivery.