Design and development of heterogeneous catalysts for sustainable formic acid-mediated alkylation of aromatics
Source abstract
Abstract
The alkylation reaction of aromatic compounds gains considerable attention because of its wide application in bulk and fine chemical production. Developing green alkylation reagents and efficient alkylation routes is the goal pursued by researchers. As a recyclable carbon carrier and hydrogen storage medium, formic acid is expected to be a widely used alkylation reagent because of its high reactivity and various functional groups. The decomposition route of formic acid dehydration or dehydrogenation and the adsorption mechanism of formate or carboxylate are expected to match the alkylation reactions of a wide range of substrates, thereby placing high demands on active site design. Accordingly, this review presents the current state of the art and outlook regarding the heterogeneously catalytic alkylation reaction of aromatics using sustainable formic acid. The future research directions for developing new heterogeneous catalysts with transformational technologies, including machine-learning-assisted catalyst optimization, are prospected.
Source: openalex_inverted_index · Quality: baseline
Research context
OpenAlex topics: Carbon dioxide utilization in catalysis · Asymmetric Hydrogenation and Catalysis · Catalysis and Hydrodesulfurization Studies
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (92)
Show source-provided references
1. Arene diversification through distal C(sp2)-H functionalization10.1126/science.abd5992 ↗
2. Advances in Rhodium-catalyzed oxidative arene alkenylation10.1021/acs.accounts.0c00036 ↗
3. 3d-Metal catalyzed N- and C-alkylation reactions via borrowing hydrogen or hydrogen autotransfer10.1021/acs.chemrev.8b00306 ↗
4. Transition-metal-catalyzed C–H alkylation using alkenes10.1021/acs.chemrev.6b00574 ↗
5. A review of new developments in the Friedel–Crafts alkylation–From green chemistry to asymmetric catalysis10.3762/bjoc.6.6 ↗
6. Beyond Friedel and Crafts: innate alkylation of C−H bonds in arenes10.1002/anie.201806631 ↗
7. Catalytic reductive N-alkylations using CO2 and carboxylic acid derivatives: recent progress and developments10.1002/anie.201810121 ↗
8. Toluene methylation with syngas to para-xylene by bifunctional ZnZrOx-HZSM-5 catalysts10.1016/S1872-2067(21)63975-X ↗
9. Synthesis of durene by methylation of 1,2,4-trimethylbenzene with syngas over bifunctional CuZnZrOx–HZSM-5 catalysts10.1039/D2CY00037G ↗
10. Selective methylation of toluene using CO2 and H2 to para-xylene10.1126/sciadv.aba5433 ↗
11. Steering CO2 hydrogenation coupled with benzene alkylation toward ethylbenzene and propylbenzene using a dual-bed catalyst system
12. Catalytic methylation of aromatic hydrocarbons using CO2/H2 over Re/TiO2 and H-MOR catalysts10.1002/cctc.202000036 ↗
13. Recent trends in upgrading of CO2 as a C1 reactant in N- and C-methylation reactions10.1002/ajoc.202200270 ↗
14. Utilization of CO2 as a C1 building block for catalytic methylation reactions10.1021/acscatal.6b02715 ↗
15. Formic acid as a hydrogen source – recent developments and future trends10.1039/c2ee21928j ↗
16. Carbon dioxide and formic acid—the couple for environmental-friendly hydrogen storage?10.1039/b907569k ↗
17. Review on recent progress and reactor set-ups for hydrogen production from formic acid decomposition
18. Progress of fundamental mechanism of formic acid decomposition and electrooxidation10.1016/j.jechem.2022.02.017 ↗
19. CO2 utilization: developments in conversion processes10.1016/j.petlm.2016.11.003 ↗
20. Thermocatalytic formic acid dehydrogenation: recent advances and emerging trends10.1039/D1TA05910F ↗
21. Development of effective catalysts for hydrogen storage technology using formic acid
22. Enabling storage and utilization of low-carbon electricity: power to formic acid10.1039/D0EE03011B ↗
23. Liquid organic and inorganic chemical hydrides for high-capacity hydrogen storage10.1039/C4EE03690E ↗
24. Green carbon science: efficient carbon resource processing, utilization, and recycling towards carbon neutrality
25. Green carbon science: keeping the pace in practice10.1002/anie.202210095 ↗
26. Luo · 2007
27. A highly selective and stable ZnO-ZrO2 solid solution catalyst for CO2 hydrogenation to methanol10.1126/sciadv.1701290 ↗
28. Wuts · 2006
29. A new facile method for the synthesis of 1-arylimidazole-5-carboxylates10.1016/S0040-4039(00)00910-2 ↗
30. ZnO as a new catalyst for N-formylation of amines under solvent-free conditions10.1021/jo060847z ↗
31. Nano rod-shaped and reusable basic Al2O3 catalyst for N-formylation of amines under solvent-free conditions: a novel, practical and convenient ‘NOSE’ approach10.1039/c2gc16020j ↗
32. Co3O4 nanoparticles prepared by oxidative precipitation method: an efficient and reusable heterogeneous catalyst for N-formylation of amines10.1007/s11164-016-2631-7 ↗
33. A capable cobalt nano-catalyst for the N-formylation of various amines and its biological activity studies10.1002/aoc.3874 ↗
34. Efficient N-formylation of primary aromatic amines using novel solid acid magnetic nanocatalyst10.1039/D0RA07476D ↗
35. Sulfonic acid supported on hydroxyapatite-encapsulated-γ-Fe2O3 nanocrystallites as a magnetically Brønsted acid for N-formylation of amines10.1016/j.apcata.2010.01.020 ↗
36. Phosphotungstic acid supported on silica-coated CoFe2O4 nanoparticles: an efficient and magnetically-recoverable catalyst for N-formylation of amines under solvent-free conditions10.1016/j.molcata.2015.05.009 ↗
37. Polyphosphoric acid supported on silica-coated NiFe2O4 nanoparticles: an efficient and magnetically-recoverable catalyst for N-formylation of amines10.1016/j.crci.2013.07.013 ↗
38. Mesoporous silica SBA-15 functionalized with acidic deep eutectic solvent: a highly active heterogeneous N-formylation catalyst under solvent-free conditions10.1002/aoc.3901 ↗
39. Preparation, characterization and application of nanosized CuO/HZSM-5 as an efficient and heterogeneous catalyst for the N-formylation of amines at room temperature10.1016/j.jcis.2016.02.062 ↗
40. Preparation and catalytic evaluation of a palladium catalyst deposited over modified clinoptilolite (Pd@MCP) for chemoselective N-formylation and N-acylation of amines10.1016/j.molstruc.2020.129076 ↗
41. Direct conversion of aryl nitro compounds to formanilides under catalytic transfer hydrogenation conditions10.1016/S0040-4039(01)00049-1 ↗
42. A highly water-dispersible/magnetically separable palladium catalyst: selective transfer hydrogenation or direct reductive N-formylation of nitroarenes in water10.1002/cplu.201500302 ↗
43. Supported palladium nanoparticles catalyzed reductive carbonylation of nitroarenes to N-arylformamides10.1002/adsc.201700944 ↗
44. Gold-catalyzed reductive transformation of nitro compounds using formic acid: mild, efficient, and versatile10.1002/cssc.201500869 ↗
45. A versatile cobalt catalyst for the reductive amination of carbonyl compounds with nitro compounds by transfer hydrogenation10.1016/j.apcatb.2017.04.026 ↗
46. High performance of a cobalt-nitrogen complex for the reduction and reductive coupling of nitro compounds into amines and their derivatives10.1126/sciadv.1601945 ↗
47. One-pot selective N-formylation of nitroarenes to formamides catalyzed by core–shell structured cobalt nanoparticles10.1039/C8CC05285A ↗
48. Cobalt nanoparticles anchoring on nitrogen doped carbon with excellent performances for transfer hydrogenation of nitrocompounds to primary amines and N-substituted formamides with formic acid10.1016/j.catcom.2019.105747 ↗
49. Atomically dispersed Zn-Nx sites in N-doped carbon for reductive N-formylation of nitroarenes with formic acid10.1002/cctc.201902109 ↗
50. Direct hydrogenation and one-pot reductive amidation of nitro compounds over Pd/ZnO nanoparticles as a recyclable and heterogeneous catalyst10.1016/j.apsusc.2014.10.131 ↗
51. Pd/C-catalyzed reductive formylation of indoles and quinolines using formic acid10.1055/s-0030-1259978 ↗
52. Heterogeneous gold-catalyzed selective reductive transformation of quinolines with formic acid10.1002/adsc.201400721 ↗
53. Selective cobalt nanoparticles for catalytic transfer hydrogenation of N-heteroarenes10.1039/C7SC02062G ↗
54. Ordered porous nitrogen-doped carbon matrix with atomically dispersed cobalt sites as an efficient catalyst for dehydrogenation and transfer hydrogenation of N-heterocycles10.1002/anie.201805467 ↗
55. Solvent-dependent, formic acid-mediated, selective reduction and reductive N-formylation of N-heterocyclic arenes with sustainable cobalt-embedded N-doped porous carbon catalyst10.1021/acssuschemeng.9b02307 ↗
56. Fieser · 1955
57. A practical and convenient procedure for the N-formylation of amines using formic acid10.5012/bkcs.2002.23.1.149 ↗
58. Solvent-free preparation of amides from acids and primary amines under microwave irradiation10.1016/S0040-4020(02)00085-6 ↗
59. Microwave promoted energy-efficient N-formylation with aqueous formic acid10.1016/j.tetlet.2006.04.148 ↗
60. Highly efficient formylation of alcohols, thiols and aniline derivatives by a heterogeneous (HCOOH/SiO2) system under microwave irradiation and solvent-free conditions
61. Magnesium oxide as an efficient catalyst for CO2 fixation and N-formylation reactions under ambient conditions
62. Anthemis xylopoda flowers aqueous extract assisted in situ green synthesis of Cu nanoparticles supported on natural Natrolite zeolite for N-formylation of amines at room temperature under environmentally benign reaction conditions10.1016/j.jcis.2015.08.040 ↗
63. Acetylation of phenols, anilines, and thiols using silica sulfuric acid under solvent-free conditions
64. A convenient method for the N-formylation of amines at room temperature using TiO2-P25 or sulfated titania10.1016/j.molcata.2010.11.002 ↗
65. Synthesis of nano ZnO: a catalyst for N-formylation of aromatic amines and biodiesel application10.2174/2405461505666200316121735 ↗
66. A general procedure for mild and rapid reduction of aliphatic and aromatic nitro compounds using ammonium formate as a catalytic hydrogen transfer agent10.1016/S0040-4039(01)91034-2 ↗
67. Heterogenized cobalt oxide catalysts for nitroarene reduction by pyrolysis of molecularly defined complexes10.1038/nchem.1645 ↗
68. Understanding the structure-performance relationship of active sites at atomic scale10.1007/s12274-022-4371-x ↗
69. Direct N-alkylation of unprotected amino acids with alcohols10.1126/sciadv.aao6494 ↗
70. Efficient and selective N-alkylation of amines with alcohols catalysed by manganese pincer complexes10.1038/ncomms12641 ↗
71. A general catalytic methylation of amines using carbon dioxide10.1002/anie.201301349 ↗
72. Creating added value with a waste: methylation of amines with CO2 and H210.1002/anie.201310337 ↗
73. Ruthenium-catalyzed direct methylation of primary and secondary aromatic amines using carbon dioxide and molecular hydrogen10.1002/anie.201304656 ↗
74. Methylation of amines, nitrobenzenes and aromatic nitriles with carbon dioxide and molecular hydrogen10.1039/C3SC52676C ↗
75. General catalytic methylation of amines with formic acid under mild reaction conditions10.1002/chem.201402124 ↗
76. Catalytic methylation of aromatic amines with formic acid as the unique carbon and hydrogen source10.1039/C4CC05908E ↗
77. Boron-catalyzed N-alkylation of amines using carboxylic acids10.1002/anie.201503879 ↗
78. Copper(II)-catalyzed selective reductive methylation of amines with formic acid: an option for indirect utilization of CO210.1021/acs.orglett.7b00551 ↗
79. Tailored cobalt-catalysts for reductive alkylation of anilines with carboxylic acids under mild conditions10.1002/anie.201806132 ↗
80. Air-tolerant direct reductive N-methylation of amines using formic acid via simple inorganic base catalysis10.1016/j.cclet.2019.04.064 ↗
81. Efficient and selective N-methylation of nitroarenes under mild reaction conditions10.1002/chem.201702783 ↗
82. Utilization of renewable formic acid from lignocellulosic biomass for the selective hydrogenation and/or N-methylation10.1002/cctc.202101099 ↗
83. Formic acid disproportionation into formaldehyde triggered by vanadium complexes with iridium catalysis under mild conditions in N-methylation10.1039/D1GC00275A ↗
84. Methylation of aromatic amines and imines using formic acid over a heterogeneous Pt/C catalyst10.1039/C6CY00674D ↗
85. Platinum nanoparticles as recyclable heterogeneous catalyst for selective methylation of amines and imines with formic acid: indirect utilization of CO2
86. Heterogeneous PdAg alloy catalyst for selective methylation of aromatic amines with formic acid under an additive-free and solvothermal one-pot condition10.1038/am.2015.116 ↗
87. Additive-free selective methylation of secondary amines with formic acid over a Pd/In2O3 catalyst10.1039/D1CY01626A ↗
88. Alkylation of benzene by esters by the Friedel—crafts reaction10.1021/ja01270a043 ↗
89. Metal-free catalysis of sustainable Friedel–Crafts reactions: direct activation of benzene by carbon nitrides to avoid the use of metal chlorides and halogenated compounds10.1039/B608532F ↗
90. Chemical synthesis of mesoporous carbon nitrides using hard templates and their use as a metal-free catalyst for Friedel–Crafts reaction of benzene10.1002/anie.200600412 ↗
91. Catalytic methylation of m-xylene, toluene, and benzene using CO2 and H2 over TiO2-supported Re and zeolite catalysts: machine-learning-assisted catalyst optimization10.1021/acscatal.0c05661 ↗
92. Methanol synthesis from CO2/CO mixture on Cu–Zn catalysts from microkinetics-guided machine learning pathway search10.1021/jacs.2c06044 ↗