Recent Advances in the Efficient Synthesis of Useful Amines from Biomass-Based Furan Compounds and Their Derivatives over Heterogeneous Catalysts

Bio-based furanic oxygenates represent a well-known class of lignocellulosic biomass-derived platform molecules. In the presence of H2 and different nitrogen sources, these versatile building blocks can be transformed into valuable amine compounds via reductive amination or hydrogen-borrowing amination mechanisms, yet they still face many challenges due to the co-existence of many side-reactions, such as direct hydrogenation, polymerization and cyclization. Hence, catalysts with specific structures and functions are required to achieve satisfactory yields of target amines. In recent years, heterogeneous catalytic synthesis of amines from bio-based furanic oxygenates has received extensive attention. In this review, we summarize and discuss the recent significant progress in the generation of useful amines from bio-based furanic oxygenates with H2 and different nitrogen sources over heterogeneous catalysts, according to various raw materials and reaction pathways. The key factors affecting catalytic performances, such as active metals, supports, promoters, reaction solvents and conditions, as well as the possible reaction routes and catalytic reaction mechanisms are studied and discussed in depth. Special attention is paid to the structure–activity relationship, which would be helpful for the development of more efficient and stable heterogeneous catalysts. Moreover, the future research direction and development trend of the efficient synthesis for bio-based amines are prospected.

[1]  Z. Huang,et al.  NiCo/Al2O3 nanocatalysts for the synthesis of 5-amino-1-pentanol and 1,5-pentanediol from biomass-derived 2-hydroxytetrahydropyran , 2023, Green Chemical Engineering.

[2]  Z. Huang,et al.  Natural Attapulgite Supported Nano-Ni Catalysts for the Efficient Reductive Amination of Biomass-Derived Aldehydes and Ketones , 2023, SSRN Electronic Journal.

[3]  Y. Suh,et al.  Recent catalytic advances on the sustainable production of primary furanic amines from the one-pot reductive amination of 5-hydroxymethylfurfural. , 2022, ChemSusChem.

[4]  Z. Huang,et al.  Reductive Amination of Biomass-Derived 2-Hydroxytetrahydropyran into 5-Amino-1-Pentanol Over Hydroxylapatite Nanorod Supported Ni Catalysts , 2022, Catalysis Letters.

[5]  J. Hofmann,et al.  Modulating Catalytic Selectivity by Base Addition in Aqueous Reductive Amination of 1,6-Hexanediol Using Ru/C , 2022, ACS Sustainable Chemistry & Engineering.

[6]  Yuanyuan Wang,et al.  Efficient Conversion of Furfural to Furfural Amine Over 4ru1co/Ac Catalyst , 2022, SSRN Electronic Journal.

[7]  Haiyang Cheng,et al.  Catalytic reductive amination of furfural to furfurylamine on robust ultra-small Ni nanoparticles , 2022, Nano Research.

[8]  M. Rose,et al.  Toward Renewable Amines: Recent Advances in the Catalytic Amination of Biomass-Derived Oxygenates , 2022, ACS Catalysis.

[9]  M. Beller,et al.  Nickel-catalyzed hydrogenative coupling of nitriles and amines for general amine synthesis , 2022, Science.

[10]  Fanyong Yan,et al.  Boron Modified Cu/Al2O3 Catalysts for the Selective Reductive Amination of Levulinic Acid to N‐Substituted Pyrrolidinones , 2022, ChemCatChem.

[11]  Z. Huang,et al.  Efficient Synthesis of Pharmaceutical Intermediates from Biomass-Derived Aldehydes and Ketones over Robust NixAl Nanocatalysts , 2022, ACS Sustainable Chemistry & Engineering.

[12]  Jinzhu Chen,et al.  An Efficient Approach to Biomass-Based Tertiary Amines by Direct and Consecutive Reductive Amination of Furfural , 2022, Journal of Catalysis.

[13]  Guoqing Li,et al.  Ambient-temperature Reductive Amination of 5-Hydroxymethylfurfural over Al2O3-supported Carbon-doped Nickel Catalyst. , 2022, ChemSusChem.

[14]  Zuojun Wei,et al.  Reductive amination of 5-hydroxymethylfurfural to 2,5-bis(aminomethyl)furan over alumina-supported Ni-based catalytic systems. , 2022, ChemSusChem.

[15]  S. Saravanamurugan,et al.  Advances in the Catalytic Reductive Amination of Furfural to Furfural Amine: The Momentous Role of Active Metal Sites. , 2022, ChemSusChem.

[16]  Zhen Fang,et al.  Synergistic Catalysis of Co‐Zr/CNx Bimetallic Nanoparticles Enables Reductive Amination of Biobased Levulinic Acid , 2022, Advanced Sustainable Systems.

[17]  Michikazu Hara,et al.  Synergistic Effects of Earth-Abundant Metal-Metal Oxide Enable Reductive Amination of Carbonyls at 50 °C. , 2022, ACS applied materials & interfaces.

[18]  C. Afonso,et al.  Upgrading furanic platforms to α-enaminones: tunable continuous flow hydrogenation of bio-based cyclopentenones , 2022, Reaction Chemistry & Engineering.

[19]  Jianping Zhang,et al.  Electronic Ni-N interaction enhanced reductive amination on N-doping porous carbon supported Ni catalyst , 2022, Catalysis Science & Technology.

[20]  N. Lingaiah,et al.  Cobalt nanoparticles embedded in a nitrogen-doped carbon catalyst for reductive amination of biomass-derived furfural to furfurylamine , 2022, Sustainable Energy & Fuels.

[21]  B. Bhanage,et al.  Insights into Cascade and Sequential one pot pathways for reductive amination of aldehydes paired with bio-derived levulinic acid to N-substituted pyrrolidones using molecular hydrogen , 2022, Reaction Chemistry & Engineering.

[22]  C. Afonso,et al.  Silica-Supported Copper for the Preparation of trans-4,5-Diamino-Cyclopent-2-Enones under Continuous Flow Conditions , 2021, ACS Sustainable Chemistry & Engineering.

[23]  C. Kreyenschulte,et al.  Reductive Amination, Hydrogenation and Hydrodeoxygenation of 5‐Hydroxymethylfurfural using Silica‐supported Cobalt‐ Nanoparticles , 2021, ChemCatChem.

[24]  Jin Gao,et al.  Self-regulated catalysis for the selective synthesis of primary amines from carbonyl compounds , 2021, Green Chemistry.

[25]  Haian Xia,et al.  Recent advances in the conversion of furfural into bio-chemicals through chemo- and bio-catalysis , 2021, RSC advances.

[26]  Jianguo Liu,et al.  Earth-abundant metal-catalyzed reductive amination: recent advances and prospect for future catalysis. , 2021, Chemistry, an Asian journal.

[27]  S. Zhong,et al.  Selective Catalysis for the Reductive Amination of Furfural Towards Furfurylamine by the Graphene-Co-Shelled Cobalt Nanoparticles , 2021, Green Chemistry.

[28]  Tao Zhang,et al.  Highly selective and robust single-atom catalyst Ru1/NC for reductive amination of aldehydes/ketones , 2021, Nature Communications.

[29]  M. Bukhtiyarova,et al.  Reductive amination of levulinic acid or its derivatives to pyrrolidones over heterogeneous catalysts in the batch and continuous flow reactors: A review , 2021 .

[30]  M. Ding,et al.  Facile and Efficient Synthesis of Primary Amines via Reductive Amination over a Ni/Al2O3 Catalyst , 2021 .

[31]  Ligong Chen,et al.  Efficient catalytic amination of diols to diamines over Cu/ZnO/γ-Al2O3 , 2021 .

[32]  R. Luque,et al.  Earth-abundant 3d-transition-metal catalysts for lignocellulosic biomass conversion. , 2021, Chemical Society reviews.

[33]  Yong Yang,et al.  Intrinsic mechanism of active metal dependent primary amine selectivity in the reductive amination of carbonyl compounds , 2021 .

[34]  N. Yan,et al.  Expanding the Boundary of Biorefinery: Organonitrogen Chemicals from Biomass. , 2021, Accounts of chemical research.

[35]  Z. Huang,et al.  Reductive amination of bio-based 2-hydroxytetrahydropyran to 5-Amino-1-pentanol over nano-Ni–Al2O3 catalysts , 2021 .

[36]  Jinjia Wei,et al.  Direct Amination of Biomass‐based Furfuryl Alcohol and 5‐(Aminomethyl)‐2‐furanmethanol with NH3 over Hydrotalcite‐derived Nickel Catalysts via the Hydrogen‐borrowing Strategy , 2021 .

[37]  Katsutoshi Sato,et al.  One-pot synthesis of pyrrolidones from levulinic acid and amines/nitroarenes/nitriles over the Ir-PVP catalyst , 2020, Green Chemistry.

[38]  A. Riisager,et al.  Sustainable access to renewable N-containing chemicals from reductive amination of biomass-derived platform compounds , 2020, Green Chemistry.

[39]  Tao Zhang,et al.  Modulating trans-imination and hydrogenation towards the highly selective production of primary diamines from dialdehydes , 2020 .

[40]  M. Bukhtiyarova,et al.  Two-Step One-Pot Reductive Amination of Furanic Aldehydes Using CuAlOx Catalyst in a Flow Reactor , 2020, Molecules.

[41]  Michikazu Hara,et al.  Effects of ruthenium hydride species on primary amine synthesis by direct amination of alcohols over a heterogeneous Ru catalyst , 2020, Chemical science.

[42]  R. Kempe,et al.  Transition-Metal-Catalyzed Reductive Amination Employing Hydrogen. , 2020, Chemical reviews.

[43]  M. Beller,et al.  Catalytic reductive aminations using molecular hydrogen for synthesis of different kinds of amines. , 2020, Chemical Society reviews.

[44]  P. Luis,et al.  Continuous Flow Upgrading of Selected C2-C6 Platform Chemicals Derived from Biomass. , 2020, Chemical reviews.

[45]  O. Ersen,et al.  A multifaceted role of a mobile bismuth promoter in alcohol amination over cobalt catalysts , 2020, Green Chemistry.

[46]  A. Khodakov,et al.  Alcohol amination over titania-supported ruthenium nanoparticles , 2020 .

[47]  Zhimin Liu,et al.  Ambient reductive synthesis of N-heterocyclic compounds over cellulose-derived carbon supported Pt nanocatalyst under H2 atmosphere , 2020 .

[48]  Xi Chen,et al.  Lignocellulosic Biomass Upgrading into Valuable Nitrogen-Containing Compounds by Heterogeneous Catalysts , 2020, Industrial & Engineering Chemistry Research.

[49]  B. Han,et al.  Ambient-Temperature Synthesis of Primary Amines via Reductive Amination of Carbonyl Compounds , 2020, ACS Catalysis.

[50]  R. Luque,et al.  Recent catalytic routes for the preparation and the upgrading of biomass derived furfural and 5-hydroxymethylfurfural. , 2020, Chemical Society reviews.

[51]  H. Shan,et al.  Preliminary evidence from a multicenter prospective observational study of the safety and efficacy of chloroquine for the treatment of COVID-19 , 2020, medRxiv.

[52]  J. Qiao,et al.  Dose selection of chloroquine phosphate for treatment of COVID-19 based on a physiologically based pharmacokinetic model , 2020, Acta Pharmaceutica Sinica B.

[53]  Srinivas Darbha,et al.  Solid catalysts for conversion of furfural and its derivatives to alkanediols , 2020 .

[54]  Xun Hu,et al.  Efficient Synthesis of 5-Amino-1-pentanol from Biomass-Derived Dihydropyran over Hydrotalcite-Based Ni–Mg3AlOx Catalysts , 2020 .

[55]  Hailong Liu,et al.  Effective synthesis of 5-amino-1-pentanol by reductive amination of biomass-derived 2-hydroxytetrahydropyran over supported Ni catalysts , 2020, Chinese Journal of Catalysis.

[56]  Xuan Yang,et al.  Selectivity Control in Catalytic Reductive Amination of Furfural to Furfurylamine on Supported Catalysts , 2020 .

[57]  Shuliang Yang,et al.  Efficient reductive amination of HMF with well dispersed Pd nanoparticles immobilized in a porous MOF/polymer composite , 2020 .

[58]  M. Pera‐Titus,et al.  Direct catalytic conversion of furfural to furan-derived amines in the presence of Ru based catalyst. , 2020, ChemSusChem.

[59]  Tao Zhang,et al.  Selective Hydrogenation over Supported Metal Catalysts: From Nanoparticles to Single Atoms. , 2019, Chemical reviews.

[60]  S. Furukawa,et al.  Organonitrogen Chemicals from Oxygen-Containing Feedstock over Heterogeneous Catalysts , 2020 .

[61]  S. Streiff,et al.  Highly selective synthesis of 2,5-bis(aminomethyl)furan via catalytic amination of 5-(hydroxymethyl)furfural with NH3 over a bifunctional catalyst , 2019, RSC advances.

[62]  Jinjia Wei,et al.  Selective Synthesis of Furfurylamine by Reductive Amination of Furfural over Raney Cobalt , 2019, ChemCatChem.

[63]  Xiao-hui Liu,et al.  Morphology‐Tuned Activity of Ru/Nb2O5 Catalysts for Ketone Reductive Amination , 2019, ChemCatChem.

[64]  Tiefeng Wang,et al.  Highly Selective Hydrogenation of Furfural to Cyclopentanone over a NiFe Bimetallic Catalyst in a Methanol/Water Solution with a Solvent Effect , 2019, ACS Sustainable Chemistry & Engineering.

[65]  Zuojun Wei,et al.  A Comprehensive Study on the Reductive Amination of 5‐Hydroxymethylfurfural into 2,5‐Bisaminomethylfuran over Raney Ni Through DFT Calculations , 2019, ChemCatChem.

[66]  Putla Sudarsanam,et al.  Advances in porous and nanoscale catalysts for viable biomass conversion. , 2019, Chemical Society reviews.

[67]  A. Bell,et al.  Propanol Amination over Supported Nickel Catalysts: Reaction Mechanism and Role of the Support , 2019, ACS Catalysis.

[68]  A. Corma,et al.  Chemicals from Biomass: Selective Synthesis of N-Substituted Furfuryl Amines by the One-Pot Direct Reductive Amination of Furanic Aldehydes , 2019, ACS Sustainable Chemistry & Engineering.

[69]  B. Han,et al.  Ambient Reductive Amination of Levulinic Acid to Pyrrolidones over Pt Nanocatalysts on Porous TiO2 Nanosheets. , 2019, Journal of the American Chemical Society.

[70]  M. Pera‐Titus,et al.  Reductive Amination of Furanic Aldehydes in Aqueous Solution over Versatile NiyAlOx Catalysts , 2019, ACS omega.

[71]  Michikazu Hara,et al.  Low-Temperature Reductive Amination of Carbonyl Compounds over Ru Deposited on Nb2O5·nH2O , 2019, ACS Sustainable Chemistry & Engineering.

[72]  B. Sels,et al.  Functionalised heterogeneous catalysts for sustainable biomass valorisation. , 2018, Chemical Society reviews.

[73]  R. Luque,et al.  Benign-by-Design Orange Peel-Templated Nanocatalysts for Continuous Flow Conversion of Levulinic Acid to N-Heterocycles , 2018, ACS Sustainable Chemistry & Engineering.

[74]  A. Khodakov,et al.  Structure-Sensitive and Insensitive Reactions in Alcohol Amination over Nonsupported Ru Nanoparticles , 2018, ACS Catalysis.

[75]  Hong-yu Zhang,et al.  Conversion of levulinic acid to N-substituted pyrrolidinones over a nonnoble bimetallic catalyst Cu15Pr3/Al2O3 , 2018, Catalysis Communications.

[76]  S. Royer,et al.  How Catalysts and Experimental Conditions Determine the Selective Hydroconversion of Furfural and 5-Hydroxymethylfurfural. , 2018, Chemical reviews.

[77]  Xianhai Zeng,et al.  Preparation of 5‐(Aminomethyl)‐2‐furanmethanol by direct reductive amination of 5‐Hydroxymethylfurfural with aqueous ammonia over the Ni/SBA‐15 catalyst , 2018 .

[78]  Jiping Ma,et al.  Selective synthesis of 2,5-bis(aminomethyl)furan via enhancing the catalytic dehydration–hydrogenation of 2,5-diformylfuran dioxime , 2018 .

[79]  A. C. Fernandes,et al.  One-pot synthesis of amines from biomass resources catalyzed by HReO4 , 2018 .

[80]  Tao Zhang,et al.  Heterogeneous single-atom catalysis , 2018, Nature Reviews Chemistry.

[81]  Takashi Toyao,et al.  Direct Synthesis of Lactams from Keto Acids, Nitriles, and H2 by Heterogeneous Pt Catalysts , 2018 .

[82]  F. Shi,et al.  Sustainable Catalytic Amination of Diols: From Cycloamination to Monoamination , 2018 .

[83]  Edit Cséfalvay,et al.  Catalytic Conversion of Carbohydrates to Initial Platform Chemicals: Chemistry and Sustainability. , 2017, Chemical reviews.

[84]  Xianhai Zeng,et al.  Synthesis of bis(amino)furans from biomass based 5-hydroxymethyl furfural , 2018 .

[85]  B. Sels,et al.  Bio-based amines through sustainable heterogeneous catalysis , 2017 .

[86]  T. Ramalho,et al.  Reductive amination of levulinic acid to different pyrrolidones on Ir/SiO2-SO3H: Elucidation of reaction mechanism , 2017 .

[87]  H. Neumann,et al.  MOF-derived cobalt nanoparticles catalyze a general synthesis of amines , 2017, Science.

[88]  C. Maravelias,et al.  New catalytic strategies for α,ω-diols production from lignocellulosic biomass. , 2017, Faraday discussions.

[89]  Zuojun Wei,et al.  Switchable synthesis of furfurylamine and tetrahydrofurfurylamine from furfuryl alcohol over RANEY® nickel , 2017 .

[90]  Michikazu Hara,et al.  Electronic Effect of Ruthenium Nanoparticles on Efficient Reductive Amination of Carbonyl Compounds. , 2017, Journal of the American Chemical Society.

[91]  Guoxiong Wang,et al.  Zirconium Oxide Supported Palladium Nanoparticles as a Highly Efficient Catalyst in the Hydrogenation–Amination of Levulinic Acid to Pyrrolidones , 2017 .

[92]  Yunqi Li,et al.  Highly Stable Porous-Carbon-Coated Ni Catalysts for the Reductive Amination of Levulinic Acid via an Unconventional Pathway , 2017 .

[93]  M. Rose,et al.  Is water a suitable solvent for the catalytic amination of alcohols , 2017 .

[94]  Tong Liu,et al.  Reductive amination of 1,6-hexanediol with Ru/Al2O3 catalyst in supercritical ammonia , 2017, Science China Chemistry.

[95]  Tao Zhang,et al.  Production of Primary Amines by Reductive Amination of Biomass-Derived Aldehydes/Ketones. , 2017, Angewandte Chemie.

[96]  J. Pascault,et al.  Biobased Amines: From Synthesis to Polymers; Present and Future. , 2016, Chemical reviews.

[97]  Tiefeng Wang,et al.  Furfural: A Promising Platform Compound for Sustainable Production of C4 and C5 Chemicals , 2016 .

[98]  M. Ojeda,et al.  Furfural: a renewable and versatile platform molecule for the synthesis of chemicals and fuels , 2016 .

[99]  P. Dhepe,et al.  Solid acid catalyzed synthesis of furans from carbohydrates , 2016 .

[100]  Max B. Braun,et al.  Continuous Reductive Amination of Biomass-Derived Molecules over Carbonized Filter Paper-Supported FeNi Alloy. , 2015, ChemSusChem.

[101]  G. Huber,et al.  Catalytic Transformation of Lignin for the Production of Chemicals and Fuels. , 2015, Chemical reviews.

[102]  M. Pera‐Titus,et al.  Hexamethylenediamine (HMDA) from fossil- vs. bio-based routes: an economic and life cycle assessment comparative study , 2015 .

[103]  A. Corma,et al.  Chemicals from Biomass: Chemoselective Reductive Amination of Ethyl Levulinate with Amines , 2015 .

[104]  Kee-In Lee,et al.  Preparation of 2,5-Bis(Aminomethyl)Furan by Direct Reductive Amination of 2,5-Diformylfuran over Nickel-Raney Catalysts , 2015 .

[105]  D. M. Alonso,et al.  Selective Production of Levulinic Acid from Furfuryl Alcohol in THF Solvent Systems over H-ZSM-5 , 2015 .

[106]  Kai Yan,et al.  Production, properties and catalytic hydrogenation of furfural to fuel additives and value-added chemicals , 2014 .

[107]  F. B. Passos,et al.  Reductive amination of furfural over Me/SiO2 - SO3H (Me: Pt, Ir, Au) catalysts , 2014 .

[108]  S. H. Siddiki,et al.  Heterogeneous Pt Catalysts for Reductive Amination of Levulinic Acid to Pyrrolidones , 2014 .

[109]  Yugen Zhang,et al.  Hydroxymethylfurfural production from bioresources: past, present and future , 2014 .

[110]  M. Pera‐Titus,et al.  Catalytic amination of biomass-based alcohols. , 2014, ChemSusChem.

[111]  R. Sheldon Green and sustainable manufacture of chemicals from biomass: state of the art , 2014 .

[112]  R. Batey,et al.  A short total synthesis of the marine sponge pyrrole-2-aminoimidazole alkaloid (±)-agelastatin A. , 2013, Angewandte Chemie.

[113]  Yanliang Yang,et al.  Conversion of furfural into cyclopentanone over Ni–Cu bimetallic catalysts , 2013 .

[114]  M. Meier,et al.  Sustainable routes to polyurethane precursors , 2013 .

[115]  M. Mura,et al.  Formic Acid: A Promising Bio‐Renewable Feedstock for Fine Chemicals , 2012 .

[116]  Nikolaos Dimitratos,et al.  Designing bimetallic catalysts for a green and sustainable future. , 2012, Chemical Society reviews.

[117]  Stephanie G. Wettstein,et al.  Bimetallic catalysts for upgrading of biomass to fuels and chemicals. , 2012, Chemical Society reviews.

[118]  Shijie Liu,et al.  Catalytic conversion of biomass-derived carbohydrates into fuels and chemicals via furanic aldehydes , 2012 .

[119]  Md. Imteyaz Alam,et al.  Advances in conversion of hemicellulosic biomass to furfural and upgrading to biofuels , 2012 .

[120]  P. Gallezot,et al.  Conversion of biomass to selected chemical products. , 2012, Chemical Society reviews.

[121]  Joseph J. Bozell,et al.  Technology development for the production of biobased products from biorefinery carbohydrates—the US Department of Energy’s “Top 10” revisited , 2010 .

[122]  K. Raghavan,et al.  Amino cyclization of terminal (α,ω)-diols over modified ZSM-5 catalysts☆ , 2002 .

[123]  F. Lichtenthaler,et al.  Unsaturated O- and N-heterocycles from carbohydrate feedstocks. , 2002, Accounts of chemical research.

[124]  Alessandro Gandini,et al.  Furans in polymer chemistry , 1997 .