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4‐Dialkylaminopyridines as Highly Active Acylation Catalysts. [New synthetic method (25)]
Author(s) -
Höfle Gerhard,
Steglich Wolfgang,
Vorbrüggen Helmut
Publication year - 1978
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.197805691
Subject(s) - acylation , chemistry , pyridine , nucleophile , catalysis , organic chemistry , succinic anhydride , aqueous medium , combinatorial chemistry , aqueous solution
The synthesis of 4‐dialkylaminopyridines can be accomplished in two steps starting from pyridine. Compared to pyridine, these derivatives are approximately 10 4 times more active when used as acylation catalysts. Dialkylaminopyridines are being used with ever‐increasing frequency for acylation reactions which proceed either incompletely or not at all in pyridine. This article reviews the various possible applications of 4‐dialkylaminopyridines in terpene, steroid, carbohydrate and nucleoside chemistry as well as in the transformation of amino acids into α‐acyl aminoketones and polymerization of isocyanates. In addition, N ‐substituted 4‐dialkylaminopyridinium salts can be used for the transfer of sensitive groups to nucleophiles in aqueous medium. The exceptional catalytic effect of these derivatives, even in non‐polar solvents, is due, in part, to the formation of high concentrations of N ‐acylpyridinium salts which are present in solution as loosely‐bound, highly reactive ion pairs.