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Acid-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

Acid-base catalysis is the acceleration of a chemical reaction by proton transfer to or from the substrate in the rate-determining or product-determining step, so that an acid, a base, or a pair of acidic and basic sites stabilizes the transition state relative to the uncatalyzed path [1][2]. In catalysis and oxidation chemistry the concept is bounded by that proton-transfer elementary step as the catalytic event, and it includes both specific catalysis (by H+ or OH− of the medium) and general catalysis (by buffer acids and bases that are present in the transition state). Essential features are a donor and an acceptor of the proton, a defined timing of proton transfer relative to heavy-atom motion, and regeneration of the acid and base so that they are not consumed. Bifunctional acid-base catalysts place the two sites in a single molecular architecture, as in designed organocatalysts for the direct aldol reaction, so that enolate formation and carbonyl activation occur in one assembly [3]. The same proton-transfer logic operates at enzymatic active sites, including ribozymes and glycosidases, where nucleophilic attack is coupled to general acid-base assistance [1][4]. The concept is distinguished from nucleophilic catalysis, in which the catalyst forms a covalent adduct with the substrate, and from Lewis-acid catalysis, in which activation occurs by coordination of an electron pair rather than by proton transfer.

  • acid-base catalysis
  • proton transfer
  • general acid
  • bifunctional catalysis

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

References

  1. Shu-Ichi Nakano; Durga M. Chadalavada; Philip C. Bevilacqua; General Acid-Base Catalysis in the Mechanism of a Hepatitis Delta Virus Ribozyme. Sci. 2000, 287, 1493-1497, 10.1126/science.287.5457.1493.
  2. 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.
  3. Susumu Saito; Hisashi Yamamoto; Design of Acid−Base Catalysis for the Asymmetric Direct Aldol Reaction. Acc. Chem. Res. 2004, 37, 570-579, 10.1021/ar030064p.
  4. David L Zechel; Stephen G Withers; Dissection of nucleophilic and acid–base catalysis in glycosidases. Curr. Opin. Chem. Biol. 2001, 5, 643-649, 10.1016/s1367-5931(01)00260-5.
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