Hydrogenation/Hydrolytic Ring Opening of 5-HMF by Cp*-Iridium(III) Half-Sandwich Complexes for Bioketones Synthesis

Xu, Zhanwei; Yan, Peifang; Xu, Wei; Liu, Xiumei; Xiong, Zhi; Chung, Benjamin; Jia, Songyan; Zhang, Z. Conrad

doi:10.1021/cs501874v

Cited by 63 publications

(70 citation statements)

References 44 publications

(50 reference statements)

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“…According to this result, we think that 5‐methylfurfuryl alcohol is the intermediate between 5‐methylfurfural and hexane‐2,5‐dione. In the recent work of Zhang and co‐workers, similar results were observed with the Cp*‐iridium(III) complex. It was suggested that the presence of a hydroxyl group promotes the hydrolysis of the furan ring.…”

Section: Resultssupporting

confidence: 74%

“…(Route 2 in Scheme ), 2A was prepared by acid‐catalyzed hydrolysis of 4‐(5‐methyl‐a‐furyl)‐2‐butanone ( 2D ) from the hydrogenation of the aldol‐condensation product ( 1D ) of methylfurfural and acetone. In the recent work of Zhang and co‐workers, a new method (Route 3 in Scheme ) was developed for the synthesis of 2A through aqueous‐phase hydrogenation of 1A catalyzed by bipyridine‐coordinated Cp*‐iridium(III) complexes (Cp*=1,2,3,4,5‐pentamethylcyclopenta‐1,3‐diene). Compared with the previous two routes, this new route is environmentally friendly and contains fewer steps.…”

Section: Resultsmentioning

confidence: 99%

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Synthesis of Renewable Triketones, Diketones, and Jet‐Fuel Range Cycloalkanes with 5‐Hydroxymethylfurfural and Ketones

Chen

et al. 2017

ChemSusChem

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A series of renewable C -C triketones with repeating [COCH CH ] units were synthesized in high carbon yields (ca. 90 %) by the aqueous-phase hydrogenation of the aldol-condensation products of 5-hydroxylmethylfurfural (HMF) and ketones over an Au/TiO catalyst. Compared with the reported routes, this new route has many advantages such as being environmentally friendly, having fewer steps, using a cheaper and reusable catalyst, etc. The triketones as obtained can be used as feedstocks in the production of conducting or semi-conducting polymers. Through a solvent-free intramolecular aldol condensation over solid-base catalysts, the triketones were selectively converted to diketones, which can be used as intermediates in the synthesis of useful chemicals or polymers. As another application, the tri- and diketones can also be utilized as precursors for the synthesis of jet-fuel range branched cycloalkanes with low freezing points (224-248 K) and high densities (ca. 0.81 g mL ).

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Section: Resultssupporting

confidence: 74%

Section: Resultsmentioning

confidence: 99%

Synthesis of Renewable Triketones, Diketones, and Jet‐Fuel Range Cycloalkanes with 5‐Hydroxymethylfurfural and Ketones

Chen

et al. 2017

ChemSusChem

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“…34 However, 14 Kegnaes et al studied the conversion of 5-HMF using O 2 with 2.5 bar pressure in the 15 presence of Ru(OH) x /Al 2 O 3 catalyst, achieved 25% LA at 140 °C. 51 Above results inferred that so far the hydrogenation/ring opening of furans 19 were acquired under strident reaction conditions like usage of H 2 gas with high pressure 20 and high temperature. 51 Above results inferred that so far the hydrogenation/ring opening of furans 19 were acquired under strident reaction conditions like usage of H 2 gas with high pressure 20 and high temperature.…”

mentioning

confidence: 87%

Catalytic transformation of bio-derived furans to valuable ketoacids and diketones by water-soluble ruthenium catalysts

et al. 2015

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9Bio-derived furans such as 2-furfural (furfural), 5-hydroxymethyl-2-furfual (5-HMF) and 10 5-methyl-2-furfural (5-MF) was successfully transformed to ketoacid, levulinic acid 11 (LA), and diketones, 1-hydroxyhexane-2,5-dione (1-HHD), 3-hydroxyhexane-2,5-dione 12 (3-HHD) and hexane-2,5-dione (HD), at moderate reaction conditions using water 13 soluble and recyclable 8-aminoquinoline coordinated arene-ruthenium(II) complexes. At 14 the optimized condition using 1 mol % catalyst in the presence of 12 equivalent formic 15 acid at 80 ~ 100 °C, complete conversion of furfural to LA with high selectivity was 16 achieved. Several experiments along with 1 H NMR spectral studies are described which 17 provide more insights into the mechanism of the transformation of furans to open ring 18 components. Experiment performed using structural analogues of active catalyst inferred 19 a structural-activity relationship for the observed superior catalytic activity of the 8-20 aminoquinoline coordinated arene-ruthenium(II) complex. Furthermore, due to high 21 aqueous solubility of the studied complexes, high recyclability, up to 4 catalytic runs, 22 was achieved without any significant loss of activity. Molecular identities of the studied 23 8-aminoquinoline coordinated arene-ruthenium(II) complex was also confirmed by 24 single-crystal X-ray diffraction studies. Development of new methodologies and catalysts for the transformation of biomass and 2 biomass derived compounds into biofuel components are highly desirable to reduce the 3 global dependence on the fossil fuel resources. Moreover, these transformations of 4 biomass can also produce several value added chemicals for potential applications in 5 chemical industries. However, direct usage of biomass is unsuitable so far. 1-7 In this 6 regard, furans, an important feedstock of biomass obtained by selective dehydration of 7 hexose and pentose sugar, are considered as an important resource for the production of 8 bio-based chemicals. 8-19 Furan derivatives such as 5-HMF, furfural and 5-MF are being 9 used as valuable C5/C6 resources for the synthesis of value added chemicals and biofuel 10 components based on LA, succinic acid, ketones, 1,6-hexanediol, cyclopentanone, adipic 11 acid, caprolactam, caprolactone, furoic acid and so on. 20-36 Moreover, C5-C9 alkane can 12 also be produced by the hydrolytic ring opening and complete hydrogenation of furans 13 and its aldol adducts. 36-38 14 Ketoacids and diketones have been successfully used to produce several value 15 added fine chemicals such as esters, alcohols, lactones, amines and cycloketones. 39-41 16 According to US-DOE, LA (ketoacid) has been identified as one of the 12 important 17 target chemicals in their biomass program. 41 Due to the presence of carbonyl group, 18 carboxylic group and α-H in LA, various sorts of compounds can be synthesized by 19 different type of reactions like halogenation, esterification, hydrogenation, condensation 20 etc. that can be used in drugs, agriculture, food, cosmetics and spice industry (...

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“…There were several reports on the conversion of HMF to HHD. Supported Pd, Pt and Au catalysts were proved to be effective for this conversion . Mentech and their group reported this conversion with 60% yield of HHD using Pt/C by the addition of oxalic acid for the first time .…”

Section: Introductionmentioning

confidence: 99%

Highly Selective Conversion of HMF to 1‐hydroxy‐ 2,5‐hexanedione on Pd/MIL‐101(Cr)

et al. 2019

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Saturated cyclohexene water was used as the reductant for the preparation of Pd/MIL‐101(Cr). The catalysts were characterized by XRD, N2 adsorption/desorption isotherms, XPS, TEM, FTIR, ICP‐AES and in‐situ FTIR spectra of adsorbed pyridine. The water saturated by cyclohexene was proved to be an effective reductant to produce metallic Pd catalyst. The texture of MIL‐101(Cr) was kept well after the introduction of Pd to MIL‐101(Cr). The hydrogenation of HMF to 1‐hydroxy‐2,5‐hexanedione (HHD) was conducted in water using Pd/MIL‐101(Cr) as catalyst. After reacted for 6 h at 413 K 4 MPa H2, up to 82% yield of HHD was achieved without acid additives. The MIL‐101(Cr) acted both as support and acid catalyst generated from the open Cr3+. The stability of the catalyst was investigated to find that the TOFs decreased slightly after the catalyst was used. The decline in the catalytic activity was discussed and ascribed to the condensation of intermediates on the active sites and the partly aggregate of Pd.

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Hydrogenation/Hydrolytic Ring Opening of 5-HMF by Cp*-Iridium(III) Half-Sandwich Complexes for Bioketones Synthesis

Cited by 63 publications

References 44 publications

Synthesis of Renewable Triketones, Diketones, and Jet‐Fuel Range Cycloalkanes with 5‐Hydroxymethylfurfural and Ketones

Synthesis of Renewable Triketones, Diketones, and Jet‐Fuel Range Cycloalkanes with 5‐Hydroxymethylfurfural and Ketones

Catalytic transformation of bio-derived furans to valuable ketoacids and diketones by water-soluble ruthenium catalysts

Highly Selective Conversion of HMF to 1‐hydroxy‐ 2,5‐hexanedione on Pd/MIL‐101(Cr)

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