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The Three‐Component Biginelli Reaction: A Combined Experimental and Theoretical Mechanistic Investigation
Author(s) -
De Souza Rodrigo O. M. A.,
da Penha Eduardo T. ,
Milagre Humberto M. S.,
Garden Simon J.,
Esteves Pierre M.,
Eberlin Marcos N.,
Antunes Octavio A. C.
Publication year - 2009
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200900470
Subject(s) - iminium , biginelli reaction , chemistry , electrospray ionization , component (thermodynamics) , reaction mechanism , cationic polymerization , enamine , computational chemistry , thermochemistry , knoevenagel condensation , mass spectrometry , urea , organic chemistry , ion , chromatography , catalysis , thermodynamics , physics
Biginelli reactions have been monitored by direct infusion electrospray ionization mass spectrometry (ESI‐MS) and key cationic intermediates involved in this three‐component reaction have been intercepted and further characterized by tandem MS experiments (ESI‐MS/MS). Density functional theory calculations were also used to investigate the feasibility of the major competing mechanisms proposed for the Biginelli reaction. The experimental and theoretical results were found to corroborate the iminium mechanism proposed by Folkers and Johnson, whereas no intermediates directly associated with either the more energy demanding Knoevenagel or enamine mechanisms could be intercepted.