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Item Recent advances in the preparation of levulinic esters from biomass-derived furanic and levulinic chemical platforms using heteropoly acid (HPA) catalysts(Elsevier B.V., 2021) Bhat, N.S.; Mal, S.S.; Dutta, S.The esters of biomass-derived levulinic acid (LA) have several potential applications, including cleaner-burning fuel additive, green solvent, fragrance ingredient, and a renewable chemical intermediate for downstream value addition. The levulinic esters (LEs) can be prepared by the acid-catalyzed alcoholysis of the biomass-derived furanic and levulinic chemical platforms such as LA, furfuryl alcohol (FAL), 5-(hydroxymethyl)furfural (HMF), and angelica lactone (AGL). The acid-catalyzed deconstruction of carbohydrates in an alcoholic medium affords the one-pot preparation of LEs. Choosing the right catalyst is of paramount importance for synthesizing LEs from both the economic and environmental perspectives. In this regard, heteropoly acids (HPAs), a class of polyoxometalates (POMs) bearing protons as the counter cation, have found widespread applications as acid catalysts in various organic transformations. HPAs are blessed with conducive properties such as controlled Brønsted and Lewis acidity, high thermal stability, robust structural features, non-toxic nature, tunable solubility, and less corrosiveness. Over the past several years, HPAs have found extensive applications as efficient and environment-friendly catalysts in biorefinery operations, including the synthesis of LEs. At this juncture, it is imperative to ascertain the achievements in this field to date and re-evaluate the challenges. This review attempts to provide up-to-date information about the preparation of LEs using HPA-based catalysts, critically analyze the literature cited, draw conclusions, and propose future prospects. © 2021 Elsevier B.V.Item Recent advances in the production and value addition of selected hydrophobic analogs of biomass-derived 5-(hydroxymethyl)furfural(Springer Science and Business Media Deutschland GmbH, 2023) Anchan, H.N.; Dutta, S.5-(Hydroxymethyl)furfural (HMF), produced by the acid-catalyzed dehydration of biomass-derived hexoses, is a well-recognized renewable chemical intermediate in the biorefinery research for the productions of fuels, chemicals, and materials. However, the inherent hydrophilicity and poor stability of HMF continue to disfavor its production and value addition from an economic standpoint. In this regard, the superior thermal and hydrolytic stability of the hydrophobic analogs of HMF simplify their isolation and purification from the aqueous (or polar) reaction media while enhancing their shelf life. The analogs show promises in supplanting HMF from its derivative chemistry. The halogenated derivatives of HMF, such as 5-(chloromethyl)furfural (CMF) and 5-(bromomethyl)furfural (BMF), can be produced directly from biomass in good isolated yields. The non-halogenated, hydrophobic derivatives of HMF include esters such as 5-(formyloxymethyl)furfural (FMF) and 5-(acetoxymethyl)furfural (AMF), obtained by the dehydration of carbohydrates in suitable carboxylic acids. The ethers of HMF, such as 5-(ethoxymethyl)furfural (EMF), can be produced directly by the acid-catalyzed alcoholysis of biomass. In addition, partially oxidized or reduced derivatives of HMF, such as 2,5-diformylfuran (DFF) and 5-methylfurfural (5MF), have also found significant interests as hydrophobic analogs of HMF. The production and value addition of various lipophilic analogs of HMF are rather scattered in the literature, and no comprehensive review is available in this area to date. This technical review attempts to fill that gap with up-to-date information with a critical analysis of the achievements and challenges. In this review, the production and derivative chemistry of various hydrophobic analogs of HMF have been discussed. The relative advantages and challenges associated with the preparation and value addition of various hydrophobic analogs of HMF are highlighted. Graphical abstract: [Figure not available: see fulltext.]. © 2021, The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature.Item Valorization of biomass-derived furfurals: reactivity patterns, synthetic strategies, and applications(Springer Science and Business Media Deutschland GmbH, 2023) Dutta, S.The expertise of synthetic organic chemistry accumulated over the past century has been instrumental in converting biomass to fuels, chemicals, and materials. Particular emphasis has been attributed to using eco-friendly reagents and reaction conditions by adhering to the principles of green chemistry. Catalysis remains at the heart of organic synthesis and has a ubiquitous presence in the organic chemistry literature. Not surprisingly, catalytic processes are increasingly used in the chemistry of renewables under commercially relevant and environmentally acceptable conditions. In this review, the synthesis of various biofuels and renewable chemicals from biomass-derived furfural and 5-(hydroxymethyl)furfural has been elaborated. Synthetic upgrading of furfurals has been shown in the light of chemical modifications of the reactive sites present in them. This review aims to provide a critical understanding of the influence of synthetic organic chemistry in biomass value addition via the furanic platform. This work will encourage the researchers to improve the existing synthetic pathways, develop new synthetic strategies, and broaden the scope of applications for biorenewable products. Graphical abstract: [Figure not available: see fulltext.]. © 2021, The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.Item Directional synthesis of aviation-, diesel-, and gasoline range hydrocarbon fuels by catalytic transformations of biomass components: An overview(Elsevier Ltd, 2023) Dutta, S.; Madav, V.; Joshi, G.; Naik, N.; Kumar, S.Selective conversion of heavily oxygenated biomolecules into hydrocarbon-based liquid transportation fuels with stipulated structural traits is of academic and industrial significance. This work provides an overview of producing fuel precursors from biomass components and their catalytic transformation into aviation-, diesel-, and gasoline-range hydrocarbon fuels (HCFs). Strategic applications of various organic transformations for the molecular design of targeted products have been rationalized. Construction and alteration of the carbon skeletal system in the fuel candidates via chemical-catalytic transformations have been highlighted. Emphasis has also been given to the process conditions and details of the catalysts employed in these processes. Critical analysis of the literature data presented in this review will assist the researchers in developing more proficient processes for the biorenewable production of drop-in HCFs. © 2023 Elsevier LtdItem Catalytic conversion of glucose and its biopolymers into renewable compounds by inducing C–C bond scission and formation(Springer Science and Business Media Deutschland GmbH, 2024) Anchan, H.N.; Bhat, N.S.; Vinod, N.; Prabhakar, P.S.; Dutta, S.Transportation fuels and chemicals can be produced renewably by selectively altering the carbon skeleton of biomass-derived glucose. The predominantly catalytic processes incorporate carbon–carbon (C–C) bond scission and formation reactions with concomitant defunctionalization and refunctionalization steps. The production and synthetic upgrading of various biochemicals achieved by the C–C bond-scission (C1–C5) and C–C bond-forming (> C6) reactions from glucose and its biopolymers (e.g., starch, cellulose) have been reviewed. The details of transforming glucose and its polymers into targeted biochemicals, such as mechanistic pathway, process parameters, product selectivity, and specifics of the catalysts employed, have been elaborated. The interconversions of these chemicals of commercial significance under catalytic conditions are also highlighted. This review will assist the researchers in comprehending this field from a distinct perspective, reassess the challenges, identify the research gaps, and critically appraise the emerging research avenues. © The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2022.Item Catalytic Transformation of Biomass into Sustainable Carbocycles: Recent Advances, Prospects, and Challenges(John Wiley and Sons Inc, 2025) Dutta, S.Organic compounds bearing one or more carbocycles in their molecular structure have a discernible presence in all major classes of organic products of industrial significance. However, sourcing carbocyclic compounds from exhaustible, anthropogenic carbon (e. g., petroleum) raises serious concerns about sustainability in the chemical industries. This review discusses recent advances in the renewable synthesis of carbocyclic compounds from biomass components following catalytic pathways. The mechanistic insights, process optimizations, green metrics, and alternative synthetic strategies of carbocyclic compounds have been detailed. Moreover, the renewable syntheses of carbocycles have been assessed against their existing synthetic routes from petroleum for better perspectives on their sustainability and technological preparedness. This work will assist the researchers in acquiring updated information on the sustainable synthesis of carbocyclic compounds from various biomass components, comprehending the research gaps, and developing superior synthetic processes for their commercial production. © 2024 Wiley-VCH GmbH.Item Hydrogen peroxide as a green oxidant for transforming biorenewable carbohydrates into organic chemicals of industrial significance(Elsevier B.V., 2025) Dutta, S.Biorefinery processes continue to seek sustainable reagents for organic transformations, especially for redox reactions. The liquid-phase oxidation reactions employing aqueous hydrogen peroxide (AQHP) do not necessitate an overpressure of gaseous oxidants, require relatively mild conditions, and produce water and oxygen as innocuous byproducts. AQHP is increasingly used in biomass value-addition pathways, often in the presence of a suitable homogeneous or heterogeneous catalyst, for faster kinetics and improved selectivity. This work gives an account of the recent developments in using AQHP as a green oxidant to convert carbohydrates or carbohydrate-derived chemical intermediates into organic chemicals of industrial significance under chemocatalytic and chemoenzymatic conditions. Mechanistic insights, selectivity, and scalability of the oxidation reactions of carbohydrates and carbohydrate-derived chemical building blocks involving AQHP have been elaborated. The prospects and challenges associated with carbohydrate-centric biorefinery processes using AQHP as a green oxidant have been highlighted. © 2025 Elsevier B.V.Item Catalytic synthesis of renewable chemicals from carbohydrates following pot, atom, and step-economy (PASE): An overview(Elsevier Ltd, 2025) Dutta, S.Pot, atom, and step-economy (PASE) help to improve the sustainability of synthesizing organic chemicals by reducing capital and operational expenditure, optimizing energy and materials input, and minimizing waste generation. Applying PASE to the catalytic conversion of biomass-derived carbohydrates into renewable organic chemicals could offer substantial societal, economic, and environmental incentives. This review article overviews recent developments in synthesizing selected high-value chemicals (e.g., furanics, alcohols, carboxylic acids, and esters) from biomass-derived carbohydrates following PASE. The discussion on catalysts, reaction parameters, mechanistic insights, and green metrics for specific biorenewable chemicals came intuitively. Competitive synthetic routes of carbohydrate-derived chemicals have been evaluated based on green metrics, influences of PASE on their commercial prospects have been highlighted, and future research directions have been proposed for the sustainable functioning of a carbohydrate-centric biorefinery. © 2025 Elsevier LtdItem Multifunctional roles of biogenic acids in the chemistry of renewables: From catalysts and reagents to reaction media(Elsevier Ltd, 2025) Dutta, S.There has been a growing emphasis on sourcing various chemical components, such as substrates, reagents, catalysts, and solvents, from biomass feedstock for enhanced sustainability in organic transformations. Biogenic carboxylic acids (BCAs), produced by chemocatalytic or enzymatic biomass conversion, are increasingly used in sustainable organic synthesis. Formic acid, acetic acid, lactic acid, gluconic acid, citric acid, and oxalic acid in their aqueous solution or undiluted form are increasingly used as acid catalysts, reagents, and reaction media for the chemistry of renewables. This work reviews recent advancements in this rapidly evolving field of research, highlighting significant achievements and addressing key challenges. For better clarity, the mechanistic aspects, substrate scopes, and reaction conditions have been elaborated. The analyses presented in this manuscript will help broaden the applications of BCAs in sustainable organic synthesis and biorefinery processes. © 2025 Elsevier LtdItem Production of 5-(formyloxymethyl)furfural from biomass-derived sugars using mixed acid catalysts and upgrading into value-added chemicals(Elsevier Ltd, 2020) Dutta, S.In this work, 5-(formyloxymethyl)furfural (FMF) has been produced from biomass-derived hexose sugars within a biphasic reaction mixture consisting of aqueous formic acid (85%), a strong Brønsted acid catalyst, and 1,2-dichloroethane as an organic extractant. Using a combination of aqueous hydrobromic acid and formic acid, under optimized condition (80 °C, 8 h, 10 wt% substrate loading), 68% isolated yield of FMF was obtained from fructose. FMF has been demonstrated as a renewable chemical building block for the synthesis of renewable chemicals of commercial significance such as 5-methylfurfural, 2,5-diformylfuran, and 2,5-furandicarboxylic acid in good to excellent isolated yields. © 2020 Elsevier Ltd