Formic acid as renewable reagent and product in biomass upgrading

Achour, Mahdi; Álvarez-Hernández, Débora; Ruiz-López, Estela; Megías-Sayago, Cristina; Ammari, Fatima; Ivanova, Svetlana; Centeno, Miguel Ángel

doi:10.1016/j.tgchem.2023.100020

Cited by 6 publications

(2 citation statements)

References 222 publications

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“…Formic acid represents an important downstream product that has wide applications in the chemical, textile, leather, pharmaceutical, and rubber industries. It also stands up as a safe and efficient hydrogen carrier for the upgrading of various biomass-based chemicals. , Formic acid is produced from biomass through thermochemical approaches including fast pyrolysis, acid hydrolysis, wet oxidation and catalytic oxidation. Evaluating from the formic acid yield, waste emissions, feedstock cost, and innovation potential, catalytic oxidation process exhibits the highest sustainability score and is nicely reviewed by Shen et al In addition to the widely reported V-catalyzed oxidative C–C bond cleavage, the recent representative publications related to the selective conversion of carbohydrates into formic acid are briefly reviewed herein.…”

Section: C–c Bond Cleavage Transformations Of Carbohydratesmentioning

confidence: 99%

Toward Value-Added Chemicals from Carbohydrates via C–C Bond Cleavage and Coupling Transformations

Zhang,

Liu

et al. 2024

ACS Catal.

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Renewable carbohydrates are nearly inexhaustible libraries of chemical building blocks, and significant research efforts have been devoted to their valorization to valuable chemicals in the past decades. The commonly recognized main transformation routes include dehydration and C−C bond cleavage pathways, which lead to the production of conventional platform chemicals such as 5-hydroxymethylfurfural/furfural, lactic acid/lactates, and so on. With the huge availability of carbohydrates on earth, the production of other fine chemicals is very attractive but remains sparse. This Review therefore emphasizes the utilization strategies of carbohydrates based on in situ C−C bond cleavage to lower carbon fragments, such as glycolaldehyde and erythrose, and their subsequent transformations, e.g. hydrogenation, hydrogenolysis, oxidation, nucleophilic addition, and amination. The isolation of reactive intermediates is avoided, leading to the formation of a variety of "unconventional" useful scaffolds, such as ethylene glycol, ethanol, keto-alcohols, glycolic acid, formic acid, C4 skeleton α-hydroxy esters, N-containing compounds, etc. Inspired by the transformation of active intermediates, the direct conversion of monosugars with similar structures through C−C coupling to furan-based chemicals is also briefly reviewed. The primary focus of this Review is to show the spectacular range of fine chemicals that can be accessed from carbohydrates via C−C bond cleavage and coupling approaches. A summary of the reviewed works and some opportunities and challenges within this attractive field are underlined for future research in sugar chemistry.

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Section: C–c Bond Cleavage Transformations Of Carbohydratesmentioning

confidence: 99%

Toward Value-Added Chemicals from Carbohydrates via C–C Bond Cleavage and Coupling Transformations

Zhang,

Liu

et al. 2024

ACS Catal.

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“…Hydrogen transfer using formic acid remains more favorable than the former two, but has low hydrogen content (<5 wt %) and is corrosive as per the United Nations’ globally harmonized system of categorization and labeling of substances (GHS [EC] ) . Moreover, the current industrial process of formic acid synthesis includes hydrolysis of MF catalyzed by the strong acids . Hence, starting with MF makes the process economical and sustainable.…”

mentioning

confidence: 99%

Methyl Formate, an Alternative Transfer Hydrogenating Agent for Chemoselective Reduction of N-Heteroarenes and Azoarenes

Sau,

Mahapatra,

Maji

et al. 2024

Org. Lett.

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The search for efficient molecular hydrogen precursors and their catalytic exploration is necessary for the evolution of catalytic transfer hydrogenation. Methyl formate (MF) having high hydrogen content still remains unexplored for such transformations. Herein, we disclosed a bifunctional Ir(III)-complex catalyzed chemoselective TH protocol for N-heteroarenes and azoarenes using MF. A variety of substrates including ten bioactive molecules have been synthesized under mild reaction conditions. A probable mechanistic pathway was proposed based on control experiments and mechanistic studies.

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Tunable Catalytic Reduction of Furfural with Formic Acid and Sodium Formate Into Furan and Tetrahydrofuran Derivatives

Oksanen,

van Strien,

Viertiö

et al. 2024

ChemCatChem

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Furfural is an attractive bio‐based platform chemical that has many derivatives of commercial interest. Herein, we show that the selectivity of the direct furfural reduction can be steered from 2‐methylfuran and 2‐methyltetrahydrofuran to furfuryl alcohol and tetrahydrofurfuryl alcohol by varying the ratio of formic acid and sodium formate. These reagents take the role of terminal reductants in the disclosed heterogeneous Pd‐catalysed process. We report the development and optimisation of the reaction conditions for three different products directly from furfural: 2‐methyltetrahydrofuran, tetrahydrofurfuryl alcohol and 2‐methylfuran which were obtained in 59%, 46%, and 63% selectivity, respectively. Furthermore, the protocol uses commercially available Pd/Al2O3 as catalyst and the formic acid and sodium formate can be obtained from biogenous sources.

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Formic acid as renewable reagent and product in biomass upgrading

Cited by 6 publications

References 222 publications

Toward Value-Added Chemicals from Carbohydrates via C–C Bond Cleavage and Coupling Transformations

Toward Value-Added Chemicals from Carbohydrates via C–C Bond Cleavage and Coupling Transformations

Methyl Formate, an Alternative Transfer Hydrogenating Agent for Chemoselective Reduction of N-Heteroarenes and Azoarenes

Tunable Catalytic Reduction of Furfural with Formic Acid and Sodium Formate Into Furan and Tetrahydrofuran Derivatives

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