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Review
. 2019 Jun 6;10(24):6024-6034.
doi: 10.1039/c9sc01309a. eCollection 2019 Jun 28.

Bio-based building blocks from 5-hydroxymethylfurfural via 1-hydroxyhexane-2,5-dione as intermediate

Bartosz Wozniak  1 , Sergey Tin  1 , Johannes G de Vries  1
Affiliations
Review

Bio-based building blocks from 5-hydroxymethylfurfural via 1-hydroxyhexane-2,5-dione as intermediate

Bartosz Wozniak et al. Chem Sci. .

Abstract

The limits to the supply of fossil resources and their ever increasing use forces us to think about future scenarios for fuels and chemicals. The platform chemical 5-hydroxymethyl-furfural (HMF) can be obtained from biomass in good yield and has the potential to be converted in just a few steps into a multitude of interesting products. Over the last 20 years, the conversion of HMF to 1-hydroxyhexane-2,5-dione (HHD) has been studied by several groups. It is possible to convert HMF into HHD by hydrogenation/hydrolytic ring opening reaction in aqueous phase using various heterogeneous and homogeneous catalysts. This review addresses both the state of the art of HHD synthesis, including mechanistic aspects of its formation, as well as the recent progress in the application of HHD as a building block for many useful chemicals including pyrroles, cyclopentanone derivatives and triols.

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Figures

Fig. 1
Fig. 1. Chemical structure of 5-hydroxymethylfurfural (HMF).
Scheme 1
Scheme 1. Conversion of HMF to valuable chemicals.
Fig. 2
Fig. 2. Chemical structure of 1-hydroxyhexane-2,5-dione (HHD).
Scheme 2
Scheme 2. Proposed pathway for HHD synthesis by Descotes.
Scheme 3
Scheme 3. Conversion of HMF to HHD, as proposed by Satsuma.
Fig. 3
Fig. 3. Iridium- and ruthenium-based complexes for the synthesis of HHD.
Scheme 4
Scheme 4. Proposed pathways for HHD synthesis by Zhang.
Scheme 5
Scheme 5. Proposed pathways for HHD synthesis by Fu.
Scheme 6
Scheme 6. Conversion of HMF to HHD under various reaction conditions; aisolated yield.
Fig. 4
Fig. 4. ORTEP representation of HHD showing intermolecular O–H···O hydrogen bonds.
Scheme 7
Scheme 7. Aldol condensation products starting from HHD.
Scheme 8
Scheme 8. Plausible mechanism for the conversion of HMF to HCPN via HHD.
Scheme 9
Scheme 9. Base-promoted intramolecular aldol condensation of HHD.
Scheme 10
Scheme 10. A one-pot synthesis of MCP from HMF.
Fig. 5
Fig. 5. ORTEP representation of MCP showing intermolecular O–H···O hydrogen bonds.
Scheme 11
Scheme 11. Conversion of MCP into valuable biomass-based products.
Scheme 12
Scheme 12. The Paal–Knorr synthesis of N-substituted pyrroles starting from HHD.
Fig. 6
Fig. 6. N-substituted pyrroles derived from HHD.
Scheme 13
Scheme 13. Homogeneous hydrogenation of HHD.
Scheme 14
Scheme 14. Rhenium catalysed transformations of 1,2,5-hexanetriol.
None
Bartosz Wozniak
None
Sergey Tin
None
Johannes G. de Vries
See this image and copyright information in PMC

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