Intramolecular general acid catalysis in the aminolysis of benzylpenicillin. A preferred direction of nucleophilic attack

1979 ◽  
pp. 298 ◽  
Author(s):  
Anthony F. Martin ◽  
Jeffrey J. Morris ◽  
Michael I. Page
Keyword(s):  
Acid Catalysis ◽  
Nucleophilic Attack ◽  
Preferred Direction ◽  
General Acid

Intramolecular General Acid Catalysis of Phosphate Transfer. Nucleophilic Attack by Oxyanions on the PO32-Group

2005 ◽  
Vol 127 (19) ◽  
pp. 7033-7040 ◽  
Author(s):  
Anthony J. Kirby ◽  
Neil Dutta-Roy ◽  
Davi da Silva ◽  
Jonathan M. Goodman ◽  
Marcelo F. Lima ◽  
...  
Keyword(s):  
Acid Catalysis ◽  
Nucleophilic Attack ◽  
General Acid

Efficient Intramolecular General Acid Catalysis of Nucleophilic Attack on a Phosphodiester

2006 ◽  
Vol 128 (51) ◽  
pp. 16944-16952 ◽  
Author(s):  
Anthony J. Kirby ◽  
Marcelo F. Lima ◽  
Davi da Silva ◽  
Christo D. Roussev ◽  
Faruk Nome
Keyword(s):  
Acid Catalysis ◽  
Nucleophilic Attack ◽  
General Acid

Intramolecular general acid catalysis of sulfate transfer — Nucleophilic attack by oxyanions on the SO3– group

2005 ◽  
Vol 83 (9) ◽  
pp. 1629-1636 ◽  
Author(s):  
Anthony J Kirby ◽  
José Carlos Gesser ◽  
Florian Hollfelder ◽  
Jacks P Priebe ◽  
Faruk Nome
Keyword(s):  
Hydrogen Bond ◽  
Transition State ◽  
Acid Catalysis ◽  
Nucleophilic Attack ◽  
General Acid ◽  
State Transfer ◽  
Carboxylate Anions ◽  
Mechanism Of Hydrolysis ◽  
Intramolecular Hydrogen ◽  
Hydrolysis Of

The mechanism of hydrolysis of 8-N,N-dimethylaminonaphthyl sulfate closely resembles that of the corresponding phosphate monoester. Nucleophilic attack by water on the sulfate group of the zwitterion is catalyzed by the neighbouring dimethylammonium group, acting as a particularly efficient general acid through the intramolecular hydrogen bond. This hydrogen bond is present in both reactant and product, but is strongest in the transition state. Transfer of the sulfuryl group to oxygen nucleophiles, including water and carboxylate anions, shows steric and electrostatic effects, and a sensitivity to basicity which is low, but significantly higher than expected for uncatalyzed transfer of the SO3– group.Key words: sulfate, sulfatase, intramolecular, general acid catalysis, promiscuity.

General acid catalysis in moderately concentrated aqueous sulphuric acid

1965 ◽  
Vol 39 ◽  
pp. 75 ◽  
Author(s):  
A. J. Kresge ◽  
L. E. Hakka ◽  
S. Mylonakis ◽  
Y. Sato
Keyword(s):  
Sulphuric Acid ◽  
Acid Catalysis ◽  
General Acid
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