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Full Paper
Rapid Organocatalytic Aldehyde-Aldehyde Condensation Reactions
Article first published online: 12 JUN 2007
DOI: 10.1002/ejoc.200700292
Copyright © 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Additional Information
How to Cite
Erkkilä, A. and Pihko, P. M. (2007), Rapid Organocatalytic Aldehyde-Aldehyde Condensation Reactions. Eur. J. Org. Chem., 2007: 4205–4216. doi: 10.1002/ejoc.200700292
Publication History
- Issue published online: 10 AUG 2007
- Article first published online: 12 JUN 2007
- Manuscript Received: 2 APR 2007
Funded by
- Academy of Finland. Grant Number: 203287
- Tekes
Keywords:
- Aldehydes;
- Amines;
- Synthetic methods;
- Kinetics;
- Linear free energy relationships
Abstract
We report the results of the systematic optimization of the α-methylenation of aldehydes with aqueous formaldehyde. A simple combination of a secondary amine catalyst and a weak acid co-catalyst has been identified, allowing access to α-substituted acroleins in a matter of minutes. In the absence of formaldehyde, the catalytic system promoted the self-condensation reaction of α,β-unsaturated aldehydes. Both of these reactions exhibited linear relationships between co-catalyst acidities and reaction rates. A second-order dependence of catalyst concentration was observed, pointing to the involvement of two molecules of the ammonium catalyst in the rate-determining step. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)