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Aerobic Oxidation of Cyclic Amines to Lactams Catalyzed by Ceria-Supported Nanogold

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Abstract

The oxidative transformation of cyclic amines to lactams, which are important chemical feedstocks, is efficiently catalyzed by CeO2-supported gold nanoparticles (Au/CeO2) and Aerosil 200 in the presence of an atmosphere of O2. The complete conversion of pyrrolidine was achieved in 6.5 h at 160 °C, affording a 97 % yield of the lactam product 2-pyrrolidone (γ-butyrolactam), while 2-piperidone (δ-valerolactam) was synthesized from piperidine (83 % yield) in 2.5 h. Caprolactam, the precursor to the commercially important nylon-6, was obtained from hexamethyleneimine in 37 % yield in 3 h. During the oxidation of pyrrolidine, two transient species, 5-(pyrrolidin-1-yl)-3,4-dihydro-2H-pyrrole (amidine-5) and 4-amino-1-(pyrrolidin-1-yl)butan-1-one, were observed. Both of these compounds were oxidized to 2-pyrrolidone under catalytic conditions, indicating their role as intermediates in the reaction pathway. In addition to the reactions of cyclic secondary amines, Au/CeO2 also efficiently catalyzes the oxidation of N-methyl cyclic tertiary amines to the corresponding lactams at 80 and 100 °C.

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Acknowledgments

This research was partially supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences through the Ames Laboratory (Contract No. DE-AC02-07CH11358). The authors thank Evonik Degussa Corporation for a generous donation of Aerosil 200.

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Authors and Affiliations

  1. Department of Chemistry, Iowa State University, 1605 Gilman Hall, 2415 Osborn Drive, Ames, IA, 50011-1021, USA

    Taiwo O. Dairo, Nicholas C. Nelson, Igor I. Slowing, Robert J. Angelici & L. Keith Woo

  2. U.S. D.O.E. Ames Laboratory, Ames, IA, 50011, USA

    Nicholas C. Nelson & Igor I. Slowing

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  1. Taiwo O. Dairo
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  2. Nicholas C. Nelson
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  3. Igor I. Slowing
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  5. L. Keith Woo
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Correspondence to L. Keith Woo.

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Dairo, T.O., Nelson, N.C., Slowing, I.I. et al. Aerobic Oxidation of Cyclic Amines to Lactams Catalyzed by Ceria-Supported Nanogold. Catal Lett 146, 2278–2291 (2016). https://doi.org/10.1007/s10562-016-1834-2

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  • DOI: https://doi.org/10.1007/s10562-016-1834-2

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