Homogeneous Catalyzed Valorization of Furanics: A Sustainable Bridge to Fuels and Chemicals

Padilla, Rosa; Koranchalil, Sakhitha; Nielsen, Martin

doi:10.3390/catal11111371

Cited by 17 publications

(19 citation statements)

References 235 publications

(266 reference statements)

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“…80 Furfural and HMF are bio-based renewable feedstocks, and their oxidation products are important for the implementation of future green chemical industry. 81,82 It was found that while in the presence of other pyridine-based pincer complexes furfural and HMF degraded to unidentifiable polymers, the acridine-based complexes selectively oxidized them with high yields (495%), while suppressing decomposition. Mechanistic experiments indicated that the employed aromatized complex is dearomatized in the initial step to generate complex 4, which subsequently catalyses the reaction.…”

Section: Deaminative Oxidation Of Amines To Acidsmentioning

confidence: 99%

Sustainable catalysis with fluxional acridine-based PNP pincer complexes

Kar

Milstein

2022

Chem. Commun.

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Section: Deaminative Oxidation Of Amines To Acidsmentioning

confidence: 99%

Sustainable catalysis with fluxional acridine-based PNP pincer complexes

Kar

Milstein

2022

Chem. Commun.

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“…Biomass-derived renewable aldehydes, specifically, furfural and 5-hydroxymethyl furfural (HMF), represent important chemical feedstocks that are expected to be crucial in the coming years for the sustainable production of commodity chemicals. , For example, 2,5-furandicarboxylic acid (FDCA), which can be synthesized via the complete oxidation of HMF or from furfural via oxidation and carboxylation, is a chemical that can potentially replace terephthalic acid in polymer synthesis. Our group has recently reported molecular complexes that can catalyze the oxidation of furfural to furoic acid using alkaline water as the oxidant while liberating H 2 gas (Figure b) .…”

Section: Oxidation Of Aldehydes To Carboxylic Acids Using Watermentioning

confidence: 99%

Oxidation of Organic Compounds Using Water as the Oxidant with H₂ Liberation Catalyzed by Molecular Metal Complexes

Kar

Milstein

2022

Acc. Chem. Res.

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Conspectus Oxidation reactions of organic compounds play a central role in both industrial chemical and material synthesis as well as in fine chemical and pharmaceutical synthesis. While traditional laboratory-scale oxidative syntheses have relied on the use of strong oxidizers, modern large-scale oxidation processes preferentially utilize air or pure O 2 as an oxidant, with other oxidants such as hydrogen peroxide, nitric acid, and aqueous chlorine solution also being used in some processes. The use of molecular oxygen or air as an oxidant has been very attractive in recent decades because of the abundance of air and the lack of wasteful byproduct generation. Nevertheless, the use of high-pressure air or, in particular, pure oxygen can lead to serious safety concerns with improper handling and also necessitates the use of sophisticated high-pressure reactors for the processes. Several research groups, including ours, have investigated in recent times the possibility of carrying out catalytic oxidation reactions using water as the formal oxidant, with no added conventional oxidants. Along with the abundant availability of water, these processes also generate dihydrogen gas as the reaction coproduct, which is a highly valuable fuel. Several well-defined molecular metal complexes have been reported in recent years to catalyze these unusual oxidative reactions with water. A ruthenium bipyridine-based PNN pincer complex was reported by us to catalyze the oxidation of primary alcohols to carboxylate salts with alkaline water along with H 2 liberation, followed by reports by other groups using other complexes as catalysts. At the same time, ruthenium-, iridium-, and rhodium-based complexes have been reported to catalyze aldehyde oxidation to carboxylic acids using water. Our group has combined the catalytic aqueous alcohol and aldehyde oxidation activity of a ruthenium complex to achieve the oxidation of biomass-derived renewable aldehydes such as furfural and 5-hydroxymethylfurfural (HMF) to furoic acid and furandicarboxylic acid (FDCA), respectively, using alkaline water as the oxidant, liberating H 2 . Ruthenium complexes with an acridine-based PNP ligand have also been employed by our group for the catalytic oxidation of amines to the corresponding lactams, or to carboxylic acids via a deaminative route, using water. Similarly, we also reported molecular complexes for the catalytic Markovnikov oxidation of alkenes to ketones using water, similar to Wacker-type oxidation, which, however, does not require any terminal oxidant and produces H 2 as the coproduct. At the same time, the oxidation of enol ethers to the corresponding esters with water has also been reported. This account will highlight these recent advances where water was used as an oxidant to carry out selective oxidation reactions of organic compounds, catalyzed by well-defined molecular complexes, with H 2 lib...

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“…Owing to the negative consequences of fossil fuel use, intensive research is ongoing, focusing on transitioning toward a renewable framework for fuel and materials production. − Furfural and 5-hydroxymethyl furfural (HMF) are chemical feedstocks produced by hydrolysis of biomass waste. − Because of their renewable nature, the synthesis of commodity chemicals from furfural and HMF has garnered increasing attention. − Among many products obtainable from furfural and HMF, their oxidation products, furoic acid and furan dicarboxylic acid (FDCA), respectively, hold particular interest (Figure A). Furoic acid has many applications including plastic plasticizer, food preservative, pharmaceutical intermediate, and FDCA precursor, and has potential applications in optics technology because of its unique crystal properties, with large-scale synthesis plants operated by multiple companies. − Similarly, FDCA is a promising renewable alternative to terephthalic acid for polymers synthesis .…”

Section: Introductionmentioning

confidence: 99%

Catalytic Furfural/5-Hydroxymethyl Furfural Oxidation to Furoic Acid/Furan-2,5-dicarboxylic Acid with H₂ Production Using Alkaline Water as the Formal Oxidant

et al. 2022

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Furfural and 5-hydroxymethyl furfural (HMF) are abundantly available biomass-derived renewable chemical feedstocks, and their oxidation to furoic acid and furan-2,5-dicarboxylic acid (FDCA), respectively, is a research area with huge prospective applications in food, cosmetics, optics, and renewable polymer industries. Water-based oxidation of furfural/HMF is a lucrative approach for simultaneous generation of H 2 and furoic acid/FDCA. However, this process is currently limited to (photo)electrochemical methods that can be challenging to control, improve, and scale up. Herein, we report well-defined ruthenium pincer catalysts for direct homogeneous oxidation of furfural/HMF to furoic acid/FDCA, using alkaline water as the formal oxidant while producing pure H 2 as the reaction byproduct. Mechanistic studies indicate that the ruthenium complex not only catalyzes the aqueous oxidation but also actively suppresses background decomposition by facilitating initial Tishchenko coupling of substrates, which is crucial for reaction selectivity. With further improvement, this process can be used in scaled-up facilities for a simultaneous renewable building block and fuel production.

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Homogeneous Catalyzed Valorization of Furanics: A Sustainable Bridge to Fuels and Chemicals

Cited by 17 publications

References 235 publications

Sustainable catalysis with fluxional acridine-based PNP pincer complexes

Sustainable catalysis with fluxional acridine-based PNP pincer complexes

Oxidation of Organic Compounds Using Water as the Oxidant with H₂ Liberation Catalyzed by Molecular Metal Complexes

Catalytic Furfural/5-Hydroxymethyl Furfural Oxidation to Furoic Acid/Furan-2,5-dicarboxylic Acid with H₂ Production Using Alkaline Water as the Formal Oxidant

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Homogeneous Catalyzed Valorization of Furanics: A Sustainable Bridge to Fuels and Chemicals

Cited by 17 publications

References 235 publications

Sustainable catalysis with fluxional acridine-based PNP pincer complexes

Sustainable catalysis with fluxional acridine-based PNP pincer complexes

Oxidation of Organic Compounds Using Water as the Oxidant with H2 Liberation Catalyzed by Molecular Metal Complexes

Catalytic Furfural/5-Hydroxymethyl Furfural Oxidation to Furoic Acid/Furan-2,5-dicarboxylic Acid with H2 Production Using Alkaline Water as the Formal Oxidant

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Oxidation of Organic Compounds Using Water as the Oxidant with H₂ Liberation Catalyzed by Molecular Metal Complexes

Catalytic Furfural/5-Hydroxymethyl Furfural Oxidation to Furoic Acid/Furan-2,5-dicarboxylic Acid with H₂ Production Using Alkaline Water as the Formal Oxidant