Efficient route for the construction of polycyclic systems from bioderived HMF

Kucherov, Fedor A.; Galkin, Konstantin I.; Gordeev, Evgeniy G.; Ananikov, Valentine P.

doi:10.1039/c7gc02211e

Cited by 65 publications

(60 citation statements)

References 48 publications

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“…The diastereomeric configuration was determined by 1 H-NMR and NOE experiments. After considering the NMR data confirmed by the X-ray analysis of HMF-derived norcantharimide analogues obtained in the previous study [ 27 ], the spatial structure of the Diels–Alder adducts was confirmed (see the Supplementary Materials ). Chemical shifts of the diastereomeric protons at the articulated position were characterized by a singlet at ~3.5–3.7 ppm in the 1 H-NMR spectra, while the signals of the appropriate protons in the exo products (compounds norcantharimide [ 28 ] and 10 -exo) were observed in the stronger magnetic fields at ~2.9–3.1 ppm.…”

Section: Resultsmentioning

confidence: 59%

“…For evaluation of the synthetic potential of the furan ring in the prepared amines, we synthesized norcantharimides 9 – 12 , which were bio-derived analogues of the anticancer drug norcantharidin. We used a modified one-pot protocol based on the Diels–Alder reaction of compounds 6 – 8 with alkenes, followed by hydrogenation of the formed double bond, as reported recently [ 27 ]. The Diels–Alder reactions were performed in THF media at room temperature and monitored by NMR.…”

Section: Resultsmentioning

confidence: 99%

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Facile Chemical Access to Biologically Active Norcantharidin Derivatives from Biomass

et al. 2017

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Reductive amination of 2,5-diformylfuran (DFF) was used to implement the transition from bio-derived 5-hydroxymethylfurfural (HMF) to pharmaceuticals. The synthesized bis(aminomethyl)furans were utilized as building blocks for the construction of new derivatives with structural cores of naturally occurring biologically active compounds. Using the one-pot procedure, which included the Diels–Alder reaction followed by hydrogenation of the double bond, bio-derived analogues of the anticancer drug norcantharidin were obtained. The cyclization process was diastereoselective, and resulted in the formation of tricyclic products with the endo configuration. Analysis of cytotoxycity for the resulting tricyclic amine-containing compounds showed an increase of anticancer activity as compared with the unsubstituted norcantharimide.

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Section: Resultsmentioning

confidence: 59%

Section: Resultsmentioning

confidence: 99%

Facile Chemical Access to Biologically Active Norcantharidin Derivatives from Biomass

et al. 2017

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“…The presence of two aldehydes groups offers many possibilities for further modification via Wittig reaction, Schiff bases formation, aldol condensation, etc. [24,25] Despite this promise, few reports make use of this compound partly owing to its current high retail price (123 £.g À 1 Sigma Merck accessed 10/3/20) and instability upon prolonged storage. Additionally, the synthesis of DFF from HMF commonly requires molecular oxygen or expensive transition metal (co)-catalyst (e. g. Ru) which further reduces the applicability of DFF-derived reaction at a higher scale.…”

Section: Resultsmentioning

confidence: 99%

Work‐hardening Photopolymer from Renewable Photoactive 3,3’‐(2,5‐Furandiyl)bisacrylic Acid

et al. 2020

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The design of a photopolymer around a renewable furan‐derived chromophore is presented herein. An optimised semi‐continuous oxidation method using MnO2 affords 2,5‐diformylfuran from 5‐(hydroxymethyl)furfural in gram quantities, allowing the subsequent synthesis of 3,3’‐(2,5‐furandiyl)bisacrylic acid in good yield and excellent stereoselectivity. The photoactivity of the diester of this monomer is confirmed by reaction under UV irradiation, and the proposed [2+2] cycloaddition mechanism supported further by TD‐DFT calculations. Oligoesters of the photoreactive furan diacid with various aliphatic diols are prepared via chemo‐ and enzyme‐catalysed polycondensation. The latter enzyme‐catalysed (Candida antarctica lipase B) method results in the highest Mn (3.6 kDa), suggesting milder conditions employed with this protocol minimised unwanted side reactions, including untimely [2+2] cycloadditions, whilst preserving the monomer's photoactivity and stereoisomerism. The photoreactive polyester is solvent cast into a film where subsequent initiator‐free UV curing leads to an impressive increase in the material stiffness, with work‐hardening characteristics observed during tensile strength testing.

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“…. 5-HMF is a promising and versatile biomass-based platform molecule from biorefinery carbohydrates, which can be used to produce various chemicals and liquid fuels currently derived from nonrenewable fossil resources [293][294][295][296]. It is worth noting that the production of 5-HMF from renewable cellulose has become an integral part of biorefinery and attracted extensive attention in recent years .…”

Section: -Hydroxymethylfurfural (5-hmf)mentioning

confidence: 99%

Chemocatalytic Conversion of Cellulose into Key Platform Chemicals

Liu

et al. 2018

International Journal of Polymer Science

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Chemocatalytic transformation of lignocellulosic biomass to value-added chemicals has attracted global interest in order to build up sustainable societies. Cellulose, the first most abundant constituent of lignocellulosic biomass, has received extensive attention for its comprehensive utilization of resource, such as its catalytic conversion into high value-added chemicals and fuels (e.g., HMF, DMF, and isosorbide). However, the low reactivity of cellulose has prevented its use in chemical industry due to stable chemical structure and poor solubility in common solvents over the cellulose. Recently, homogeneous or heterogeneous catalysis for the conversion of cellulose has been expected to overcome this issue, because various types of pretreatment and homogeneous or heterogeneous catalysts can be designed and applied in a wide range of reaction conditions. In this review, we show the present situation and perspective of homogeneous or heterogeneous catalysis for the direct conversion of cellulose into useful platform chemicals.

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Efficient route for the construction of polycyclic systems from bioderived HMF

Abstract: Efficient one-pot synthesis of tricyclic compounds from biobased 5-hydroxymethylfurfural (HMF) is described using a [4 + 2] cycloaddition reaction.

Cited by 65 publications

References 48 publications

Facile Chemical Access to Biologically Active Norcantharidin Derivatives from Biomass

Facile Chemical Access to Biologically Active Norcantharidin Derivatives from Biomass

Work‐hardening Photopolymer from Renewable Photoactive 3,3’‐(2,5‐Furandiyl)bisacrylic Acid

Chemocatalytic Conversion of Cellulose into Key Platform Chemicals

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