Dualistic Nature of the Mechanism of the Morita−Baylis−Hillman Reaction Probed by Electrospray Ionization Mass Spectrometry

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• 作者：Giovanni W. Amarante ; Humberto M. S. Milagre ; Boniek G. Vaz ; Bruno R. Vilach Ferreira ; Marcos N. Eberlin ; Fernando Coelho
• 刊名：Journal of Organic Chemistry
• 出版年：2009
• 出版时间：April 17, 2009
• 年：2009
• 卷：74
• 期：8
• 页码：3031-3037
• 全文大小：359K
• 年卷期：v.74,no.8(April 17, 2009)
• ISSN：1520-6904

文摘

The Morita−Baylis−Hillman (MBH) reaction allows chemists to form new σ C−C bonds in a single-step straightforward manner and thus to construct densely functionalized molecules for further chemical manipulation. Using electrospray ionization for transferring ions directly from solution to the gas phase, and mass (and tandem mass) spectrometry for mass and structural assignments, new key intermediates for the rate-determining step of the MBH reaction have been successfully intercepted and structurally characterized. These ESI-MS data provide experimental evidence supporting recent suggestions, based on kinetic experiments and theoretical calculations, for the dualist nature of the proton-transfer step of the MBH mechanism.