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Base Catalysis: History
Please note this is an old version of this entry, which may differ significantly from the current revision.
Subjects: Chemistry, Organic
Contributor: Helena Kang

Acceleration of a chemical transformation by a species that accepts a proton or donates an electron pair to a substrate defines base catalysis. In general base catalysis a proton is partially transferred in the rate-determining step and the catalyst is regenerated; in specific base catalysis the active nucleophile is the lyate ion formed in a prior equilibrium. Lewis base catalysis is the complementary closed-shell process in which the catalyst binds a Lewis-acidic site (a carbonyl carbon, a silicon center, or a π-acidic metal) and thereby activates the substrate without net proton transfer [1]. Dual catalytic systems may combine a Lewis base with a photoredox cycle so that the two catalysts jointly generate the nucleophilic and electrophilic partners of a C–C bond-forming step [2]. In ribonucleic acid catalysis, general acid–base catalysis likewise proceeds by concerted proton transfer at the phosphodiester, underscoring that the defining elementary act is proton shuttling rather than metal redox chemistry [3]. The concept excludes stoichiometric use of a strong base as a reagent: the base must be turned over. It is complementary to acid catalysis, which activates by proton donation or Lewis-acid coordination [1].

  • base catalysis
  • Lewis base catalysis
  • general base catalysis
  • proton transfer

Catalysis and Oxidation Reactions • Catalysis • Chemical Engineering • Physical Sciences

References

  1. Scott E. Denmark; Gregory L. Beutner; Lewis Base Catalysis in Organic Synthesis. Angew. Chem. Int. Ed. 2008, 47, 1560-1638, 10.1002/anie.200604943.
  2. Magnus Rueping; Carlos Vila; René M. Koenigs; Konstantin Poscharny; David C. Fabry; Dual catalysis: combining photoredox and Lewis base catalysis for direct Mannich reactions. Chem. Commun. 2010, 47, 2360-2362, 10.1039/c0cc04539j.
  3. Philip C. Bevilacqua; Mechanistic Considerations for General Acid−Base Catalysis by RNA: Revisiting the Mechanism of the Hairpin Ribozyme. Biochem. 2003, 42, 2259-2265, 10.1021/bi027273m.
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