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  • Review Article
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Homogeneous catalysis for the production of low-volume, high-value chemicals from biomass

Nature Reviews Chemistry volume 2, pages 35–46 (2018)Cite this article

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Abstract

The transition from petroleum to biorenewable sources of carbon to meet our energy and chemical feedstock needs is difficult, in part because these sources are so different, with petroleum being under-functionalized and biomass being over-functionalized relative to commercial chemicals. However, target lists such as the US Department of Energy’s Top 10 have converged efforts to develop the technologies needed to manufacture the most important feedstocks accessible from biorenewables. Less well defined but equally important to the economic viability of an integrated biorefinery are low-volume, high-value product streams, which would help offset the capital costs of a biorefinery. In this Review, we attempt to bring together some of the advances that could fill these niche areas, with a focus on the conversion of cellulosics into chemicals using homogeneous catalysis. The products range from high-value jet fuels to monomers for high-performance polymers and materials to pharmaceutical intermediates and cover a broad range of structural complexities.

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Fig. 1: Catalysis is the technological linchpin that will enable a fully integrated biorefinery to produce a combination of high-volume, low-value products (likely dominated by heterogeneous catalysis) for the commodity market and low-volume, high-value products for the specialty and pharmaceutical markets.
Fig. 2: Catalytic defunctionalization of cellulosics to hydrocarbon-based secondary targets.
Fig. 3: Selective B(C6F5)3-catalysed strategies for hydrosilylation of primary C–O bonds.
Fig. 4: Selective catalytic reduction of secondary C–O bonds in a cellulosic.
Fig. 5: Protecting-group-free selective catalytic decarbonylation and heterocycle formation of cellulosics.
Fig. 6: Protecting-group-free catalytic carbonyl-based coupling of cellulosics with nucleophilic nitrogen sources.
Fig. 7: Direct catalytic addition of carbon-based nucleophiles to d-glucose.
Fig. 8: Catalytic C–C bond formations on cellulosic biorefinery primary chemicals.
Fig. 9: Selective redox neutral transformations of bio-inspired chemicals and cellulosics.

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Acknowledgements

The authors thank the US Department of Energy Office of Basic Energy Sciences for their support of this work (DE-FG02-05ER15630). J.A.D. thanks Elon University for teaching relief during manuscript preparation.

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  1. Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC, USA

    Trandon A. Bender & Michel R. Gagné

  2. Department of Chemistry, Elon University, Elon, NC, USA

    Jennifer A. Dabrowski

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Glossary

Biorefinery

Infrastructure that converts biomass or biomaterials into value-added products.

Cellulosics

Materials that are derived from cellulose, typically C6 sugars.

Stereoablative

A process that removes the stereochemistry within a molecule, often by transforming a stereogenic centre to an achiral centre.

Redox neutral

A chemical reaction in which the overall oxidation state of the molecule does not change. Although these transformations are powerful, their utilization in the field of cellulosic derivatization is underexplored.

Catalyst control

A reaction in which the product outcome is dictated by the nature of the catalyst, which supersedes any biases imposed by the substrate. This may be in the form of differences in reactivity or selectivity. The pre-existing stereochemical complexity of cellulosics makes imposing control of both site-selectivity and stereoselectivity in a transformation challenging.

Substrate control

A paradigm wherein the inherent nature of the reactant dictates the product outcome. In cellulosics, the existing stereochemistry of the alcohols can often control how reactions proceed.

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Bender, T.A., Dabrowski, J.A. & Gagné, M.R. Homogeneous catalysis for the production of low-volume, high-value chemicals from biomass. Nat Rev Chem 2, 35–46 (2018). https://doi.org/10.1038/s41570-018-0005-y

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