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Deoxydehydration of Polyols

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Selective Catalysis for Renewable Feedstocks and Chemicals

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 353))

Abstract

The development of sustainable chemical processes for the conversion of highly oxygenated biomass feedstocks to chemical products requires efficient and selective processes for partial oxygen removal and refunctionalization. Here we review the development of the deoxydehydration (DODH) reaction, which converts vicinal diols (glycols) to olefins. Uncatalyzed deoxygenative eliminations were first established. The catalyzed DODH reactions have largely employed oxo-rhenium catalysts and a variety of reductants, including PR3, dihydrogen, sulfite, and alcohols. A variety of glycol and biomass-derived polyol substrates undergo the DODH reaction in moderate to good efficiency, regioselectively, and stereoselectively. Observations regarding selectivity, mechanistic probes, and computational studies support the general operation of a catalytic process involving three basic stages: glycol condensation to an M-glycolate, reduction of the oxo-metal, glycol condensation to produce a metal-glycolate, and alkene extrusion from the reduced metal-glycolate. Recent practical developments include the discovery of non-precious V- and Mo-oxo DODH catalysis.

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Abbreviations

APR:

Ammonium perrhenate

Bn:

Benzyl

Cp:

Cyclopentadienyl

DFT:

Density functional theory

DODH:

Deoxydehydration

e.u.:

entropy

MTO:

Methyltrioxorhenium

TPB:

tris-Pyrazolylborate

TsOH:

para-Toluenesulfonic acid

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Acknowledgments

We are grateful for financial support of our research on catalytic deoxydehydration provided by the U.S. Department of Energy (Basic Energy Sciences) and by the National Science Foundation.

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, University of Oklahoma, 101 Stephenson Parkway, Norman, OK, 73019, USA

    Camille Boucher-Jacobs & Kenneth M. Nicholas

Authors
  1. Camille Boucher-Jacobs
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  2. Kenneth M. Nicholas
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Correspondence to Kenneth M. Nicholas .

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Editors and Affiliations

  1. Department of Chemistry and Biochemistry, University of Oklahoma, Norman, Oklahoma, USA

    Kenneth M. Nicholas

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Boucher-Jacobs, C., Nicholas, K.M. (2014). Deoxydehydration of Polyols. In: Nicholas, K. (eds) Selective Catalysis for Renewable Feedstocks and Chemicals. Topics in Current Chemistry, vol 353. Springer, Cham. https://doi.org/10.1007/128_2014_537

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