Review

4-Dialkylaminopyridines as Highly Active Acylation Catalysts. [New synthetic method (25)]†‡

  1. Priv.-Doz. Dr. Gerhard Höfle1,
  2. Prof. Dr. Wolfgang Steglich2,
  3. Prof. Dr. Helmut Vorbrüggen3,*

Article first published online: 22 DEC 2003

DOI: 10.1002/anie.197805691

Issue

Angewandte Chemie International Edition in English

Angewandte Chemie International Edition in English

Volume 17, Issue 8, pages 569–583, August 1978

Additional Information

How to Cite

Höfle, G., Steglich, W. and Vorbrüggen, H. (1978), 4-Dialkylaminopyridines as Highly Active Acylation Catalysts. [New synthetic method (25)]. Angew. Chem. Int. Ed. Engl., 17: 569–583. doi: 10.1002/anie.197805691

Author Information

  1. 1

    Organisch-Chemisches Institut der Technischen Universität, Strasse des 17. Juni 135, D-1000 Berlin 12 (Germany)

  2. 2

    Institut für Organische Chemie und Biochemie der Universität, Gerhard-Domagk-Strasse, D-5300 Bonn (Germany)

  3. 3

    Research Laboratories of Schering AG, Berlin/Bergkamen, P.O. Box 650311, D-1000 Berlin 65 (Germany)

*Research Laboratories of Schering AG, Berlin/Bergkamen, P.O. Box 650311, D-1000 Berlin 65 (Germany)

  1. †

    4-Dialkylaminopyridines as acylation catalysts, 4th Communication.—3rd Communication: G. Höfle, W. Steglich, Synthesis 1972, 619.

  2. ‡

    Pyridine syntheses, 1st Communication.—2nd Communication: H. Vorbrüggen, J. Kottwitz, K. Krolikiewicz, Chem. Ber., in preparation. This publication gives a complete survey of the various syntheses of DMAP and PPY; H. Vorbrüggen, DOS 2517774 (1975). Schering AG; Chem. Abstr. 86, 55293d (1977).

Publication History

  1. Issue published online: 22 DEC 2003
  2. Article first published online: 22 DEC 2003
  3. Manuscript Received: 10 MAY 1978

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Keywords:

  • 4-Dialkylaminopyridines;
  • Amino pyridines;
  • Acylation;
  • Catalysis;
  • Synthetic methods;
  • Pyridines

Abstract

The synthesis of 4-dialkylaminopyridines can be accomplished in two steps starting from pyridine. Compared to pyridine, these derivatives are approximately 104 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.

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