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Full Paper
The Catalytic Potential of Substituted Pyridines in Acylation Reactions: Theoretical Prediction and Experimental Validation
Article first published online: 7 FEB 2012
DOI: 10.1002/cctc.201100313
Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1867-3899/asset/cover.gif?v=1&s=a75870e8b7a2d2294add06ac7e86a42a0c6b3866 "ChemCatChem")
Additional Information
How to Cite
Larionov, E., Achrainer, F., Humin, J. and Zipse, H. (2012), The Catalytic Potential of Substituted Pyridines in Acylation Reactions: Theoretical Prediction and Experimental Validation. ChemCatChem, 4: 559–566. doi: 10.1002/cctc.201100313
Publication History
- Issue published online: 28 MAR 2012
- Article first published online: 7 FEB 2012
- Manuscript Revised: 10 NOV 2011
- Manuscript Received: 6 SEP 2011
Funded by
- Deutsche Forschungsgemeinschaft. Grant Number: SPP 1179
Keywords:
- acylation;
- density functional calculations;
- organocatalysis;
- structure-activity relationships;
- transition states
Abstract
A larger number of catalysts based on the 3,4-diaminopyridine motif have been synthesized and tested in the acetylation of tertiary alcohols. The rate data determined in these reactions together with results from previous studies were compared with theoretical data describing the ground and transition state properties of the respective catalysts. Surprisingly, it was found that the ground state data provided a better overall description of the catalytic activity than the transition state models. The latter approach clearly showed the presence of separate correlations for catalysts with small, but significant topological differences. Full analysis of the potential energy surface revealed that this owes to changes in the rate limiting step in the catalytic cycle.