Annelated Pyridines as Highly Nucleophilic and Lewis Basic Catalysts for Acylation Reactions |
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| Authors: | Raman Tandon Teresa Unzner Dr. Tobias A. Nigst Dr. Nicolas De Rycke Dr. Peter Mayer Dr. Bernd Wendt Dr. Olivier R. P. David Prof. Dr. Hendrik Zipse |
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| Affiliation: | 1. Department of Chemistry, LMU München, Butenandtsrasse 5‐13, 81377 München (Germany), Fax: (+49)?89‐2180‐77738;2. Institut Lavoisier—Versailles, UMR 8180, Université de Versailles St‐Quentin‐en‐Yvelines, 45 avenue des Etats‐Unis, 78035, Versailles (France);3. Certara, Martin‐Kollar‐Stra?e 17, 81829 München (Germany) |
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| Abstract: | New heterocyclic derivatives of 9‐azajulolidine have been synthesized and characterized with respect to their nucleophilicity and Lewis basicity. The Lewis basicity of these bases as quantified through their theoretically calculated methyl‐cation affinities correlate well with the experimentally measured reaction rates for addition to benzhydryl cations. All newly synthesized pyridines show exceptional catalytic activities in benchmark acylation reactions, which correlate only poorly with Lewis basicity or nucleophilicity parameters. A combination of Lewis basicity with charge and geometric parameters in the framework of a three‐component quantitative structure–activity relationship (QSAR) model is, however, highly predictive. |
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| Keywords: | acylation nucleophilic catalysis organocatalysis structure– activity relationships |
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