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Conversion of Furfural Derivatives to 1,4-Pentanediol and Cyclopentanol in Aqueous Medium Catalyzed by trans-[(2,9-Dipyridyl-1,10-phenanthroline)(CH3CN)2Ru](OTf)2
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    Conversion of Furfural Derivatives to 1,4-Pentanediol and Cyclopentanol in Aqueous Medium Catalyzed by trans-[(2,9-Dipyridyl-1,10-phenanthroline)(CH3CN)2Ru](OTf)2
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    • Maryanne K. Stones
      Maryanne K. Stones
      The Guelph-Waterloo-Centre for Graduate Work in Chemistry (GWC)2, Department of Chemistry, University of Guelph, 50 Stone Road East, Guelph, Ontario N1G 2W1, Canada
    • Elise M.-J. Banz Chung
      Elise M.-J. Banz Chung
      The Guelph-Waterloo-Centre for Graduate Work in Chemistry (GWC)2, Department of Chemistry, University of Guelph, 50 Stone Road East, Guelph, Ontario N1G 2W1, Canada
    • Igor Tadeu da Cunha
      Igor Tadeu da Cunha
      The Guelph-Waterloo-Centre for Graduate Work in Chemistry (GWC)2, Department of Chemistry, University of Guelph, 50 Stone Road East, Guelph, Ontario N1G 2W1, Canada
    • Ryan J. Sullivan
      Ryan J. Sullivan
      The Guelph-Waterloo-Centre for Graduate Work in Chemistry (GWC)2, Department of Chemistry, University of Guelph, 50 Stone Road East, Guelph, Ontario N1G 2W1, Canada
    • Parnian Soltanipanah
      Parnian Soltanipanah
      The Guelph-Waterloo-Centre for Graduate Work in Chemistry (GWC)2, Department of Chemistry, University of Guelph, 50 Stone Road East, Guelph, Ontario N1G 2W1, Canada
    • Megan Magee
      Megan Magee
      The Guelph-Waterloo-Centre for Graduate Work in Chemistry (GWC)2, Department of Chemistry, University of Guelph, 50 Stone Road East, Guelph, Ontario N1G 2W1, Canada
      More by Megan Magee
    • Gary J. Umphrey
      Gary J. Umphrey
      Department of Mathematics and Statistics, University of Guelph, 50 Stone Road East, Guelph, Ontario N1G 2W1, Canada
    • Cameron M. Moore
      Cameron M. Moore
      Chemistry Division, Los Alamos National Laboratory, MS J514, Los Alamos, New Mexico 87545, United States
    • Andrew D. Sutton
      Andrew D. Sutton
      Chemistry Division, Los Alamos National Laboratory, MS J514, Los Alamos, New Mexico 87545, United States
    • Marcel Schlaf*
      Marcel Schlaf
      The Guelph-Waterloo-Centre for Graduate Work in Chemistry (GWC)2, Department of Chemistry, University of Guelph, 50 Stone Road East, Guelph, Ontario N1G 2W1, Canada
      *E-mail: [email protected]
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    ACS Catalysis

    Cite this: ACS Catal. 2020, 10, 4, 2667–2683
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    https://doi.org/10.1021/acscatal.9b05055
    Published January 30, 2020
    Copyright © 2020 American Chemical Society

    Abstract

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    The complex trans-[(2,9-dipyridyl-1,10-phenanthroline)(CH3CN)2Ru](OTf)2 was synthesized and tested as a homogeneous hydrodeoxygenation catalyst for the conversion of biomass-derived furfuryl alcohol and furfuryl acetate to 1,4-pentanediol (as the primary target compound) and cyclopentanol (formed by the competing Piancatelli rearrangement) in aqueous reaction medium at elevated temperature (150–200 °C) and hydrogen pressure (800 psi = 5.12 MPa). Catalytic reactions using furfuryl alcohol as a substrate were limited by the formation of solid resins with the product yields showing a strong negative correlation with increasing substrate concentration and maximum yields of 1,4-pentanediol and cyclopentanol being 23 and 41%, respectively. A two-level full factorial design of experiments study with four independent input variables (temp., time, [cat.], [substrate]) and a center point was carried out for the conversion of furfuryl acetate, showing good reproducibility between replicates and no humin formation. This enabled a full statistical analysis of the input variable impact on product distribution and yield. The maximum yields of 1,4-pentanediol and cyclopentanol using furfuryl acetate as a substrate are 68 and 35%, respectively. The decreased self-reactivity of furfuryl acetate versus furfuryl alcohol dramatically increases the yields of target products but still shows a strong negative correlation of the yield of the desired products with increasing substrate concentration.

    Copyright © 2020 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acscatal.9b05055.

    • Compound data sheets with details of synthetic preparations and images of NMR and MS spectra (PDF)

    • Statistical analysis details for the DOE study (PDF)

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    Cited By

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    This article is cited by 24 publications.

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    ACS Catalysis

    Cite this: ACS Catal. 2020, 10, 4, 2667–2683
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acscatal.9b05055
    Published January 30, 2020
    Copyright © 2020 American Chemical Society

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