Catalysis, of acylation

In 1991, Jacobs analysed 18 examples of antibody catalysis of acyl-transfer reactions as a test of the Pauling concept, i.e. delivering catalysis by TS stabilization. The range of examples included the hydrolysis of aryl carbonates and of both aryl and alkyl esters. In some cases more than one reaction was catalysed by the same antibody, in others the same reaction was catalysed by different antibodies. 

The Catalysis of Acyl-Transfer Reactions of Reactive Esters... 68... 

Oxygen-based nucleophiles can also be employed for the catalysis of acyl transfer. For example, pyridine-A-oxide derivatives such as 4-DMAP-A-oxide have long been known as such catalysts although, interestingly, these catalophores are reportedly particularly efficient at mediating sulfonyl and phosphoryl transfer [229-230]. 

There are many reactions in which pyridines are used as bases. However in a large number of reactions only pyridine itself is reactive. a-Substituted pyridines behave differently, e.g. in the catalysis of acylation reactions with acyl chlorides or anhydrides [45]. The sterical hinderance of the a-substituents decelerates reactions in which a pyridine reacts as a nucleophile. A reaction which can be base-catalyzed by a-substituted pyridines is the addition of alcohols to hetero-cumulenes such as ketenes and isocyanates. Therefore this reaction was investigated as a model reaction for base catalysis by concave pyridines. 

Sanders and coworkers have extended the use of these cyclic porphyrin systems in the catalysis of acyl-transfer reactions [15] and hetero-Diels-Alder reactions [16]. 

Catalysis of Acyl Transfer Processes by Crown-Ether Supported Alkaline-Earth Metal Ions... 

Baldini, L., Bracchini, C., Cacciapaglia, R., Casnati, A., Mandolini, L. and Ungaro, R. (2000) Catalysis of acyl group transfer by a double-disiplacement mechanism the cleavage of aryl esters catalyzed by calixcrown-Ba complexes. Chem.-Eur. J., 6, 1322. 

Anderson, B. D., R. A. Conradi, and W. J. Lambert. 1984. Carboxyl group catalysis of acyl transfer reactions in corticosteroid 17- and 21-monoestefsPharm. Sci73 604-611. 

Dimethylaminopyridine (DMAP). Use of 4-dialkylaminopyridines for catalysis of acylation and alkylation has been reviewed (133 references). ... 

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