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Nitrilimine cycloadditions catalyzed by iron oxide nanoparticles

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Abstract

Nitrilimine cycloadditions to ethylenes, acetylenes, and activated nitriles have been exploited in the presence of catalytic amounts of oleic-acid-coated iron oxide nanoparticles (diameter = 11.9 ± 1.0 nm). The reactions were fully regioselective with monosubstituted ethylenes and ethyl cyanoformiate, while mixtures of cycloadducts were obtained in the presence of methyl propiolate. The intervention of iron oxide nanoparticles allowed carrying out the cycloadditions at milder conditions compared to the metal-free thermal processes. A labile intermediate has been proposed to explain this behavior.

Nitrilimine cycloadditions to ethylenes, acetylenes, and activated nitriles have been exploited in the presence of catalytic amounts of oleic-acid-coated iron oxide nanoparticles.

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Acknowledgements

The authors are grateful to F. Cargnoni (ISTM-CNR, Milan) for useful suggestions about the DFT calculations.

Funding

This study was funded by Regione Lombardia (RSPPTECH Project); the Italian MIUR under grant FIRB RBAP115AYN (oxides at the nanoscale: multifunctionality and applications) and the Department of Chemistry of UNIMI under grant PSR2015-1716FDEMA_09 (cycloaddition reactions catalyzed by metal oxide nanoparticles: NANOCAT).

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Authors and Affiliations

  1. Dipartimento di Chimica, Università degli Studi di Milano, via Golgi 19, 20133, Milan, Italy

    Giorgio Molteni

  2. Laboratorio di Nanotecnologie, Istituto di Scienze e Tecnologie Molecolari, Consiglio Nazionale delle Ricerche, via G. Fantoli 16/15, 20138, Milan, Italy

    Anna M. Ferretti, Sara Mondini & Alessandro Ponti

Authors
  1. Giorgio Molteni
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  2. Anna M. Ferretti
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  3. Sara Mondini
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  4. Alessandro Ponti
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Contributions

G.M. and A.P. together conceived and planned the research, discussed the results, and wrote the manuscript. G.M. carried out all the cycloadditions. A.M.F. and S.M. synthesized the nanoparticles and A.M.F. characterized them. A.P. carried out the calculations. All the authors read and approved the final manuscript.

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Correspondence to Giorgio Molteni.

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Molteni, G., Ferretti, A.M., Mondini, S. et al. Nitrilimine cycloadditions catalyzed by iron oxide nanoparticles. J Nanopart Res 20, 79 (2018). https://doi.org/10.1007/s11051-018-4184-8

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