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Rapid Organocatalytic Aldehyde‐Aldehyde Condensation Reactions
Author(s) -
Erkkilä Anniina,
Pihko Petri M.
Publication year - 2007
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200700292
Subject(s) - aldehyde , chemistry , formaldehyde , catalysis , amine gas treating , aqueous solution , organic chemistry , condensation , condensation reaction , physics , thermodynamics
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)