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Morita–Baylis–Hillman adducts as building blocks of heterocycles: a simple approach to 4-substituted pyrazolones, and mechanism investigation via ESI–MS(/MS)

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Abstract

We describe herein an efficient approach for the preparation of 4-substituted 2,3-dihydro-1H-pyrazol-3-ones starting from Morita–Baylis–Hillman adducts. These heterocycles were obtained in two or three steps as single isomers with moderate to good overall yields. One efficient and alternative methodology for the synthesis of α-methyl-β-ketoesters is also reported (up to 91 % yield). Additionally, the mechanism of formation of pyrazolones was investigated employing ESI–MS/MS reaction monitoring.

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Acknowledgments

The authors thank the São Paulo Research Foundation (FAPESP) and the Brazilian Council for Scientific and Technological Development (CNPq) for financial support. We also thank FAPESP for a post-doctoral fellowship to RCB (process FAPESP 2012/24783-1) and CNPq for fellowships to MTRJr and LAZ.

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Authors and Affiliations

  1. Laboratory of Synthesis of Natural Products and Drugs, University of Campinas, PO Box 6154, Campinas, SP, 13083-970, Brazil

    Rosimeire C. Barcelos, Lucas A. Zeoly, Manoel T. Rodrigues Jr. & Fernando Coelho

  2. Laboratory ThoMSon of Mass Spectrometry, University of Campinas, PO Box 6154, Campinas, SP, 13083-970, Brazil

    Bruno R. V. Ferreira & Marcos N. Eberlin

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  1. Rosimeire C. Barcelos
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  2. Lucas A. Zeoly
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  3. Manoel T. Rodrigues Jr.
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  4. Bruno R. V. Ferreira
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  5. Marcos N. Eberlin
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  6. Fernando Coelho
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Correspondence to Fernando Coelho.

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Barcelos, R.C., Zeoly, L.A., Rodrigues, M.T. et al. Morita–Baylis–Hillman adducts as building blocks of heterocycles: a simple approach to 4-substituted pyrazolones, and mechanism investigation via ESI–MS(/MS). Monatsh Chem 146, 1557–1570 (2015). https://doi.org/10.1007/s00706-015-1427-6

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