Probing the mechanism of direct Mannich-type α-methylenation of ketoesters via electrospray ionization mass spectrometry

Reactions promoting direct Mannich-type α-methylenation of α, β and γ-ketoesters have been monitored via electrospray ionization mass and tandem mass spectrometric experiments. Key intermediates of the catalytical cycle of this synthetically useful reaction have been intercepted and characterized. T...

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Bibliographic Details
Published in:Journal of mass spectrometry 2007-10, Vol.42 (10), p.1287-1293
Main Authors: Milagre, Cíntia D.F, Milagre, Humberto M.S, Santos, Leonardo S, Lopes, Marcelo L.A, Moran, Paulo J.S, Eberlin, Marcos N, Rodrigues, J. Augusto R
Format: Article
Language:English
Subjects:
Chemistry
electrospray ionization mass spectrometry
Exact sciences and technology
ketoesters
Kinetics and mechanisms
Organic chemistry
reaction mechanisms
Reactivity and mechanisms
α-methylenation
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Summary:Reactions promoting direct Mannich-type α-methylenation of α, β and γ-ketoesters have been monitored via electrospray ionization mass and tandem mass spectrometric experiments. Key intermediates of the catalytical cycle of this synthetically useful reaction have been intercepted and characterized. The mechanistic information provided by electrospray ionization mass spectrometry/mass spectrometry (ESI-MS/MS) guided the optimization of reaction conditions, allowing α-methyleneketoesters to be prepared in high yields (80-95%) and in high-enough purity for immediate further manipulation. Copyright © 2007 John Wiley & Sons, Ltd.
ISSN:1076-5174
1096-9888
DOI:10.1002/jms.1173