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Type: Artigo de periódico
Title: Morita-baylis-hillman Reaction: Esi-ms(/ms) Investigation With Charge Tags And Ionic Liquid Effect Origin Revealed By Dft Calculations
Author: Rodrigues T.S.
Silva V.H.C.
Lalli P.M.
De Oliveira H.C.B.
Da Silva W.A.
Coelho F.
Eberlin M.N.
Neto B.A.D.
Abstract: The use of a charge-tagged acrylate derivative bearing an imidazolium tag to study the Morita-Baylis-Hillman reaction via ESI-MS(/MS) monitoring and the effect of such tag (imidazolium cations and ion pairs) over TSs is described. The ionic nature of the substrate was meant to facilitate ESI transfer to the gas phase for direct mass spectrometric analysis. The detection and characterization of charged intermediates has suggested major reaction pathways. DFT calculations considering the effect of a polar and protic solvent (methanol), of a polar and aprotic solvent (acetonitrile), and of no solvent (gas phase) were used to predict possible TSs through a common accepted intermediate. The controversial proton transfer step, which may proceed via Aggarwals or McQuades proposals, was evaluated. Calculations predicted the formation of electrostatic intermediate complexes with both the cation and anion when charge-tagged reagents are used. These complexes contribute to the positive ionic liquid effect, and based on the formation of these unique complexes, a rationale for the ionic liquid effect is proposed. These complexes also pointed to a plausible explanation for the positive ionic liquid effect observed in several reactions that are difficult to be carried out in organic solvents but have shown a beneficial effect when performed in ionic liquids. © 2014 American Chemical Society.
Editor: American Chemical Society
Rights: fechado
Identifier DOI: 10.1021/jo500799j
Date Issue: 2014
Appears in Collections:Unicamp - Artigos e Outros Documentos

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