Table of Contents

Cover

Title Page

Chapter 1: Introduction to Room-Temperature Catalysis

1.1 Introduction
1.2 Room-Temperature Homogeneous Catalysts
1.3 Room-Temperature Heterogeneous Catalysts
1.4 Conclusions and Perspectives
References

Chapter 2: Functionalized Ionic Liquid-based Catalytic Systems with Diversified Performance Enhancements

2.1 Introduction
2.2 Functionalized ILs for Enhancing Catalytic Activity
2.3 Functionalized ILs for Improving Reaction Selectivity
2.4 Functionalized ILs for Facilitating Catalyst Recycling and Product Isolation
2.5 Functionalized ILs for Making Relay Catalysis
2.6 Cation and Anion Synergistic Catalysis in Ionic Liquids
2.7 Functionalized ILs for Aqueous Catalysis
2.8 Catalysis by Porous Poly-ILs
2.9 Functionalized IL-Based Carbon Material for Catalysis
2.10 Summary and Conclusions
References

Chapter 3: Heterogeneous Room Temperature Catalysis – Nanomaterials

3.1 Introduction
3.2 Solid-Acid-Based Nanomaterials
3.3 Grafted-Metal-Ions-Based Nanomaterial
3.4 Metal NPs-Based Nanomaterial
3.5 Metal Oxide NPs-Based Nanomaterial
3.6 Summary and Conclusions
References

Chapter 4: Biocatalysis at Room Temperature

4.1 Introduction
4.2 Transaminases
4.3 Hydrolases
4.4 Laccases
4.5 Enzymes in Ionic Liquids
References

Chapter 5: Room Temperature Catalysis Enabled by Light

5.1 Introduction
5.2 UV Photochemistry
5.3 Visible Light Photoredox Catalysis
5.4 Room Temperature Cross-Coupling Enabled by Light
5.5 Photochemistry and Microreactor Technology – A Perfect Match?
5.6 The Use of Photochemistry in Material Science
5.7 Solar Fuels
5.8 Conclusion
References

Chapter 6: Mechanochemically Enhanced Organic Transformations

6.1 Introduction
6.2 Mechanochemical Techniques and Mechanisms: Neat versus Liquid-Assisted Grinding (LAG)
6.3 Oxidation and Reduction Using Mechanochemistry
6.4 Electrocyclic Reactions: Equilibrium and Templating in Mechanochemistry
6.5 Recent Advances in Metal-Catalyzed Mechanochemical Reactions
6.6 New Frontiers in Organic Synthesis Enabled by Mechanochemistry
6.7 Conclusion and Outlook
Acknowledgments
References

Chapter 7: Palladium-Catalyzed Cross-Coupling in Continuous Flow at Room and Mild Temperature

7.1 Introduction
7.2 Suzuki Cross-Coupling in Continuous Flow
7.3 Heck Cross-Coupling in Continuous Flow
7.4 Murahashi Cross-Coupling in Continuous Flow
7.5 Concluding Remarks
References

Chapter 8: Catalysis for Environmental Applications

8.1 Introduction
8.2 Ferrate (FeO₄²⁻) for Water Treatment
8.3 Magnetically Separable Ferrite for Water Treatment
8.4 UV, Solar, and Visible Light-Activated TiO₂ Photocatalysts for Environmental Application
8.5 Catalysis for Remediation of Contaminated Groundwater and Soils
8.6 Novel Catalysis for Environmental Applications
8.7 Summary and Conclusions
Acknowledgments
Disclaimer
References

Chapter 9: Future Development in Room-Temperature Catalysis and Challenges in the Twenty-first Century

Case Study 1: Magnetic Pd Catalysts for Benzyl Alcohol Oxidation to Benzaldehyde

1.1 Introduction
1.2 Pd/MagSBA Magnetic Catalyst for Selective Benzyl Alcohol Oxidation to Benzaldehyde
1.3 Summary and Conclusions
References

Case Study 2: Development of Hydrothermally Stable Functional Materials for Sustainable Conversion of Biomass to Furan Compounds

2.1 Introduction
2.2 Metal–Organic-Framework as a Potential Catalyst for Biomass Valorization
2.3 Xylose Dehydration to Furfural Using Metal–Organic-Framework, MIL-101(Cr)
2.4 Conclusion
References

Index

End User License Agreement

List of Illustrations

Chapter 1: Introduction to Room-Temperature Catalysis

Figure 1.1 Brønsted acidic ionic liquids (BAILs) used as catalyst in the synthesis of α-aminophosphonates in a one-pot, three-component reaction.
Figure 1.2 Multiple-acidic ionic liquids in the synthesis of bis-indolylmethanes.
Scheme 1.1 Synthetic procedure for [Ni(P^R₂N^R′₂)₂(CH₃CN)]²⁺ complexes.
Figure 1.3 WERSA isolation procedure from rice straw.
Scheme 1.2 Synthesis of carboranes with homogeneous silver catalysts.
Scheme 1.3 Plausible mechanism for the gold-catalyzed oxidative homocoupling of terminal alkynes.
Figure 1.4 (a) Overview of the PdCNT catalyst assembly; (b) structure of DANTA; (c) structure of PDADMAC.
Scheme 1.4 Preparation of Silica-3p-TPP.
Figure 1.5 Encapsulation of PVP and Pd in the 3D interconnected pore channels of KIT-5.
Scheme 1.5 Schematic representation of the synthesis of SiO₂/Pd–NP/porous-SiO₂ core–shell–shell nanospheres.
Figure 1.6 TEM images of (a) SiO₂/Pd–NP core–shell nanospheres with 20 nm Pd–NP chemisorbed on aminopropyl-modified silica nanospheres and the corresponding (b) SiO₂/Pd–NP/SiO₂ core–shell–shell nanospheres, and (c) SiO₂/Pd–NP/porous-SiO₂ core–shell–shell nanospheres etched for 120 min.
Scheme 1.6 A schematic illustration of the formation and shape evolution of the Pd/Fe₃O₄ spheres in the whole synthetic process.
Scheme 1.7 General reaction pathways for the oxidation of GLY and PG.
Scheme 1.8 Proposed reaction mechanism for polyols oxidation catalyzed by PtAu–starch/HT. (Tongsakul et al. 2013 [67]. Reproduced with permission of American Chemical Society.)
Figure 1.7 Structure of monoliths 1−10.
Scheme 1.9 Huisgen [3+2] cycloaddition.
Scheme 1.10 Synthesis of silica-functionalized Cu(I) iodide [SiO₂–CuI].
Scheme 1.11 Suggested mechanism for the Cu/AlO(OH)–H₅IO₆ catalytic system.
Figure 1.8 The pictures of (a) CuNPs@SCF dispersed in the reaction solution, (b) the reaction solution at the end of the reaction after the application of lab magnet.
Scheme 1.12 Grafting of phthalocyanine on crystalline nanocellulose: (i) EPTMAC, NaOH; (ii) Cu–tetrasulfonate phthalocyanine. Inset: Digital photos of NCC–PC (solid) and NCC–PC (aqueous suspension).
Figure 1.9 TEM photographs describing the morphology of the catalyst: (a) silica nanoparticles used as a support, (b) Au seeds, and (c) Au nanoparticles decorating the surface of the silica after amino–silane coupling. (d) Histogram (N = 220) showing the particle-size distribution of the Au nanoparticles.

Chapter 2: Functionalized Ionic Liquid-based Catalytic Systems with Diversified Performance Enhancements

Figure 2.1 Schematic illustration of acid catalysis with Brønsted acid ILs. (BAIL: brønsted acid ionic liquid; SFBAIL: sulfonyl functionalized brønsted acid ionic liquid).
Scheme 2.1 Nucleophilic substitution of benzhydrol and phenylacetylene over different acidic ILs.
Figure 2.2 Phase behavior of IL catalyst in the abovementioned reaction (a) IL 1a; (b) Forbes' IL; (c) congener of 1a without sulfonyl group, the photos were taken at 100 °C.
Scheme 2.2 Reductive alkylation of indole with cyclic ketones by using IL 1a as catalyst.
Figure 2.3 Color change due to the condensation reaction at interface between CH₂Cl₂ and Brønsted acid IL.
Scheme 2.3 Biphasic synthesis of porphyrin.
Figure 2.4 Esterification of citric acid with n-butanol over Brønsted acid IL contains heteropolyacid anion; (a) catalyst (solid at bottom), citric acid (white solid in the middle), and alcohol (liquid in the upper phase) before mixing; (b) homogeneous mixture during the reaction; (c) heterogeneous mixture near completion of the reaction; (d) at the end of the reaction, the catalyst precipitated out.
Figure 2.5 Polyoxometalate-based ILs remain in the bottom of vessel. Esterification illustrated by the catalyst: (a) before reaction; (b) during the reaction; (c) at the end of the reaction.
Scheme 2.4 Conversion of fructose into 5-alkoxymethylfurfural ethers in heterogeneous system.
Figure 2.6 General principle of thermo-regulated phase separable catalysis (TPSC)-based AGET ATRP. (r.t: roomtemperature).
Figure 2.7 Hydrogenation of aromatic ketone in a choline–betainium IL with the aid of palladium catalyst.
Scheme 2.5 Hydrogenation of phenol to cyclohexane catalyzed by Rh nanoparticles in Brønsted acid IL.
Figure 2.8 Conversion of tetrahydrofurfurylacetone via combination of Ru and Brønsted acid IL in a one-pot two-step system. (FF: furfural; FFA: furfuralacetone; THFA: 4-(2-tetrahydrofuryl)-2-butanol).
Scheme 2.6 Cooperative nucleophilic–electrophilic organocatalysis by IL.
Scheme 2.7 Conversions of hemicelluloses to furfural by Brønsted acid IL in aqueous system.
Scheme 2.8 Pinacol rearrangements of triphenylethylene glycol in IL and water using microwave.
Figure 2.9 Schematic illustration of MPIL-based heterogeneous catalysts.
Figure 2.10 Schematic structure of the magnetic nanoparticles supported multilayered cross-linked poly(ionic liquid). (AIBN: 2,2′-Azobis(2-methylpropionitrile).
Figure 2.11 Synthesis of metal/metal oxide-supported carbon catalysts from ILs using hard-templating method.
Figure 2.12 Ionic liquid precursors used to synthesize the N-doped carbon materials.
Figure 2.13 One-pot synthesis of metal-supported N-doped carbon catalytic materials from metal-containing IL precursors.

Chapter 3: Heterogeneous Room Temperature Catalysis – Nanomaterials

Scheme 3.1 Cyanosilylation of aromatic aldehydes/ketones catalyzed by catalyst 1.
Scheme 3.2 GO catalyzed Michael-type Friedel–Crafts addition of indoles.
Scheme 3.3 G-SO₃H catalyzed hydration of propylene oxide.
Scheme 3.4 Nanoferrite–Ni catalyzed hydrogenation reactions.
Scheme 3.5 Asymmetric allylation of 4-nitrobenzaldehyde with allyltributyltin catalyzed by nano-Fe₃O₄–Pd–NHC complex.
Scheme 3.6 Sonogashira coupling of benzoyl chloride with phenylacetylene catalyzed by Pd(OAc)₂@dendrimer.
Scheme 3.7 (a) Hydrogenation of olefins and (b) reduction of nitrobenzene by Pd(II) grafted on MONT, (c) schematic representation of the NHC-based ligand.
Scheme 3.8 Suzuki–Miyaura coupling reactions catalyzed by the chiral Pd NPs.
Scheme 3.9 PVP-stabilized Au/Pd alloy NPs-catalyzed Ullmann coupling of 4-Chlorotoluene.
Scheme 3.10 Polymer 1 (x/y/z 28 : 34 : 38).
Scheme 3.11 Oxidation of (±)-1-phenylethanol using the PI Au NCs.
Scheme 3.12 Stille reaction catalyzed by dendrimer-encapsulated Pd NPs.
Scheme 3.13 Chemoselective reduction of aromatic nitroarenes catalyzed by NAP-Mg–Au(0). Conversion/selectivity valves and reaction time are listed below each product.
Scheme 3.14 The imination of nitroarenes using aldehydes and carbon monoxide by Au/TiO₂.
Scheme 3.15 Reduction of nitroarenes to anilines catalyzed by Pd@NAC-800.
Scheme 3.16 rGO-Co₃₀Pd₇₀-catalyzed tandem reduction of various aromatic nitro or nitriles or carbonyl compounds.
Scheme 3.17 AuCNT-catalyzed oxidation of various silanes.
Scheme 3.18 AuCNT-catalyzed N-formylation of secondary/primary amines.
Scheme 3.19 Laser-driven amide formation between benzaldehyde and morpholine (a) and tandem oxidation/amidation reaction between benzyl alcohol and morpholine to 4-benzoylmorpholine (b) catalyzed by Au/SiO₂ at room temperature.
Scheme 3.20 Pd-MAGSNC catalyzed Suzuki–Miyaura coupling of aryl bromides and phenylboronic acid.
Scheme 3.21 Selective examples of aerobic oxidation of alcohols using Au@PMO catalytic system.
Scheme 3.22 The reduction of 4-nitrophenol by Ni/SNTs.
Scheme 3.23 The oxidation of 1-phenylethanol by Au/MIL-101 (CD/PVP).
Scheme 3.24 The oxidation of cinnamyl alcohol by Pd/MIL-101.
Scheme 3.25 The oxidation of alcohol catalyzed by Pt@MOF-177 under solvent- and base-free condition at room temperature.
Scheme 3.26 Hydrogenation of hydroxy-aromatic derivatives with 5 wt% Pd/MIL-101.
Scheme 3.27 Encapsulation of Pd NPs in UiO-67 via preincorporation of metal precursor method.
Scheme 3.28 Hydrogenation of (a) tetraphenylethylene, (b) styrene, and (c) nitrobenzene.
Scheme 3.29 Encapsulation of PdNi NPs in UiO-67 via the in situ metal precursor incorporation method.
Scheme 3.30 Room temperature reduction of nitrobenzene for aniline formation by PdNi-in-UiO-67.
Scheme 3.31 Knoevenagel condensation of 4-nitrobenzaldehyde and malononitrile and subsequent selective hydrogenation catalyzed by Pd@IRMOF-3 core–shell nanocomposites.
Scheme 3.32 Reaction pathways in the hydrogenation of cinnamaldehyde.
Scheme 3.33 Chemoselective hydrogenation of cinnamaldehyde to hydrocinnamaldehyde.
Scheme 3.34 Deoxygenation of styrene oxide on TiO₂ particles under photoirradiation.

Chapter 4: Biocatalysis at Room Temperature

Figure 4.1 Reaction for the synthesis of l-phenylalanine catalyzed by the enzyme AAT.
Figure 4.2 Enantiomerically pure (S)-amines using ω-transaminases. (Adapted from Ref. [21].)
Figure 4.3 Complementary approaches for the preparation of enantio-enriched achiral primary amines corresponding to the reaction run forward and reverse, respectively. (a) Kinetic resolution starting with racemic (rac) amines is limited by 50% maximum yield. Nevertheless, employing pyruvate as amine acceptor shifts the reaction to the product side. (b) Theoretically, a 100% yield is possible in asymmetric synthesis from prochiral ketones if the equilibrium can be shifted appropriately. (Koszelewski et al. 2010 [22]. Reproduced with permission of Elsevier.)
Figure 4.4 Kinetic resolution of rac-1a–d using sol–gel entrapped ω-transaminase.
Figure 4.5 (R)-Valinol.
Figure 4.6 Lipase-catalyzed hydrolysis reaction [48].
Figure 4.7 Carbon–carbon bond formation through aldol addition, according to [74]).
Figure 4.8 Asymmetric aldol reaction between acetone and different aromatic aldehydes using porcine pancreatic lipase (PPL), according to [75].
Figure 4.9 Aldol addition between a tricyclic ketone and in situ-generated acetaldehyde (produced in the reaction media due to hydrolysis of vinyl acetate), according to [76].
Figure 4.10 Michael addition of 1,3-dicarbonyl compounds and an α/β-unsaturated aldehyde or ketone according to [74].
Figure 4.11 One-pot Mannich reaction between acetone, aniline, and aromatic aldehydes under aqueous conditions, according to [75].
Figure 4.12 Michael addition between different secondary amines (such as pyrrolidine, piperidine, and diethylamine) and acrylonitrile, according to [79].
Figure 4.13 Lipase-catalyzed perhydrolysis reaction according to [80].
Figure 4.14 Lipase-catalyzed epoxidation of α/β-unsaturated compounds, according to Svedendahl et al. [81].
Figure 4.15 Kinetic resolution of p-chlorostyrene oxide, according to [84].
Figure 4.16 Lipase-catalyzed enantioselective transesterification of 1-bromo-3-(4-(2-methoxy-ethyl)phenoxy)-propan-2-ol, according to [86].
Figure 4.17 Kinetic resolution according to [88].
Figure 4.18 Structure of malathion.
Figure 4.19 General structure and details of the active site of laccase (Trametes trogii laccase, PDB ID: 2HRG). The three cupredoxin-like domains (D1, D2 and D3) are shown in green, cyan, and magenta, respectively. Purple blue spheres represent copper ions and red spheres depict coordinating water molecules. The residues of the internal transfer pathway from T1 Cu to the T2/T3 trinuclear cluster are colored in yellow. Residues involved in the first coordination sphere of the catalytic coppers and their interactions (as black dashes) are also represented.
Figure 4.20 A simplified reaction mechanism of laccase oxidation of suitable substrate, using coniferyl alcohol as an example.
Figure 4.21 Kinetically controlled synthesis of phenylethyl acetate from 2-phenylethanol and vinyl acetate catalyzed by Pseudomonas cepaceae lipase.
Figure 4.22 Resolution of (±)-1 using pancreatin lipase in [C₈mim][PF₆] at room temperature [211].
Figure 4.23 Soybean peroxidase (SBP)-catalyzed polymerization of p-cresol.
Figure 4.24 A new route for enzymatic in situ saccharification in water–ionic liquid mixture.
Figure 4.25 Schematic illustration of the asymmetric whole-cell biotransformation of 2-octanone to (R)-2-octanol in a biphasic system with ionic liquids (LB-ADH: Lactobacillus brevis alcohol dehydrogenase; CB-FDH: Candida boidinii formate dehydrogenase).
Figure 4.26 The asymmetric reduction of 4′-bromo-2,2,2-trifluoroacetophenone to (R)-4′-bromo-2,2,2-trifluoroacetophenyl alcohol by alcohol dehydrogenase isolated from Rhodococcus erythropolis (ADH RE) and co-factor recycling by the glucose dehydrogenase 103 (GDH 103)-mediated oxidation of glucose.
Figure 4.27 Whole cell reaction in ionic liquid: asymmetric reduction of 4′-methoxyacetophenone.
Figure 4.28 Synthesis of chiral epichlorohydrin by CPO-catalyzed epoxidation of 3-chloropropene. (Adapted from Ref. [191].)
Figure 4.29 Esterification reaction of esculin and rutin.
Figure 4.30 Esterification of − EC with gallic acid to epicatechingallate using tannase.

Chapter 5: Room Temperature Catalysis Enabled by Light

Scheme 5.1 UV-induced photocyclizations at room temperature.
Scheme 5.2 Norrish reactions in organic synthetic photochemistry.
Scheme 5.3 Intermolecular [2+2] photocycloadditions.
Scheme 5.4 Ruthenium polypyridyl complexes as versatile visible light photoredox catalysts and their photocatalytic cycle with reductive and oxidative quenching pathways.
Scheme 5.5 Visible light photoredox catalysis for the direct coupling of N-methylmorpholine with an unfunctionalized pyridazine.
Scheme 5.6 Merging photoredox catalysis with organocatalysis to enable asymmetric organic transformations.
Scheme 5.7 Photocatalytic C−H arylation of heteroarenes with Eosin Y.
Scheme 5.8 Photoinduced copper-catalyzed Ullmann C−N coupling at room temperature.
Scheme 5.9 Room temperature C−H arylation by merging palladium and photoredox catalysis.
Scheme 5.10 Room temperature C_sp2−C_sp3 coupling by merging nickel and photoredox catalysis.
Scheme 5.11 Room temperature oxyarylation of alkenes by merging gold and photoredox catalysis.
Scheme 5.12 Intramolecular [5+2] photocycloaddition to prepare the key pyrrolo[1,2-a]azepine core required for the total synthesis of (±)-neostenine.
Scheme 5.13 Photocatalytic Stadler–Ziegler synthesis of arylsulfides in a visible light photomicroreactor.
Scheme 5.14 Continuous flow photocatalytic aerobic oxidation to produce oxytocin.
Scheme 5.15 Continuous flow singlet oxygen oxidation en route to artemisinin.
Scheme 5.16 (a) Controlled living radical polymerization of methacrylates. (b) Patterning of surfaces by using a photomask. (c) Gradient structures by using a neutral density filter.
Scheme 5.17 End group modification of maleimide functionalized poly(butyl acrylate) via a [2+2] cycloaddition reaction in batch and flow.
Scheme 5.18 (a) Schematic representation of the microfluidic flow-focusing device to prepare Janus particles. (b) Image of the setup.
Scheme 5.19 Norrish type I α-cleavage to prepare radicals that can reduce Ag⁺ to prepare Ag nanoparticles.
Scheme 5.20 Artificial photosynthesis using solar energy to split water into hydrogen and oxygen.

Chapter 6: Mechanochemically Enhanced Organic Transformations

Figure 6.1 Examples of two aldimine condensation reactions taking place by different mechanisms of mass transfer. (a) Mixing of 4-aminotoluene with 2-hydroxy-3-methoxybenzaldehyde produces an orange eutectic melt in which the reaction takes place. (b) Upon mixing with a glass rod for 2 min, the entire reaction mixture is molten. (c) The melt is of sufficiently low viscosity to be handled with a pipette. (d) The condensation of 4-methylaniline and 4-hydroxybenzaldehyde is an example of a reaction that does not take place via an intermediate liquid phase. (e) Powder X-ray diffraction (PXRD) analysis of the solid reaction mixture reveals partial formation of the product imine.
Figure 6.2 Mechanochemical synthesis of zwitterionic m-aminobenzoquinones, reported by Fang et al. [38]: (a) general reaction scheme and (b) dependence of the reaction mixture temperature on the amount of milling media, expressed as “bead height.”
Scheme 6.1 Substances involved in the oxidation of anilines to nitrobenzenes.
Scheme 6.2 Mechanochemical transformation of thioethers and thiophenes into sulfones using Oxone [48].
Scheme 6.3 Mechanochemical reduction of aldehydes and ketones by milling with NaBH₄, as described by Naimi-Jamal et al. [59].
Scheme 6.4 Ball milling reduction of methyl benzoate esters through LiBH₄ formed by in situ metathesis of NaBH₄ and LiCl [58].
Figure 6.3 (a) Mechanochemical Diels–Alder reaction of fullerene C₆₀ and anthracene; (b) the evolution of the reaction mixture during 60 min milling of C₆₀ and anthracene in a 1.2 : 1 stoichiometric ratio and (c) the evolution of the reaction mixture during 60 min milling of the previously prepared 1 : 1 Diels–Alder adduct of anthracene and C₆₀ [65].
Figure 6.4 (a) Mechanochemical Diels–Alder reaction of fullerene C₆₀ with pentacene; (b, c) steric considerations for the formation of Diels–Alder adducts based on a 2 : 1 ratio of C₆₀ and pentacene.
Figure 6.5 The mechanochemical and photochemical [2+2] dimerization of olefins directed by a resorcinol as a catalytic, hydrogen-bonding template, developed by the MacGillivray group [67, 69].
Scheme 6.5 Examples of mechanochemically conducted copper-catalyzed azide–alkyne Huisgen “click” reactions achieved by using (a) external copper(II) acetate as the catalyst and (b) copper milling equipment as the catalyst source [86, 87].
Scheme 6.6 Mechanochemical ruthenium-catalyzed olefin metathesis in a ball mill [91].
Scheme 6.7 (a) Mechanochemical synthesis of [Cp*RhCl₂]₂, the organometallic catalyst used for (b) the mechanochemical C−H activation and halogenation of o-phenylpyridine conducted in the planetary mill [98].
Scheme 6.8 Mechanochemical ball milling cyclopropanation of alkenes with diazoacetates using a silver metal foil as the source of silver catalyst [100].
Scheme 6.9 Mechanochemical synthesis of the natural product Leu-enkephalin through a seven-step sequence of solvent-free mechanochemical coupling and thermochemical deprotection steps, developed by the Lamaty group [105].
Scheme 6.10 Mechanochemical synthesis of antidiabetic sulfonyl-urea drugs reported by Tan et al. [107].
Scheme 6.11 The mechanochemically enabled synthesis of dumbbell C₁₂₀ molecule from C₆₀ using KCN, discovered by Wang et al. [110].
Scheme 6.12 Mechanochemically enabled synthesis of sulfonyl guanidines by copper-catalyzed coupling of carbodiimides and aryl sulfonamides, reported by Tan et al. [111].
Figure 6.6 Isolation of elusive aryl N-thiocarbamoylbenzotriazoles as bench-stable solids using mechanochemistry, reported by Štrukil et al. (a) the comparison of solution-based and mechanochemical milling reactivity and (b) fragment of the crystal structure of a mechanochemically prepared aryl N-thiocarbamoylbenzotriazole, identified by structure determination from X-ray powder diffraction data.

Chapter 7: Palladium-Catalyzed Cross-Coupling in Continuous Flow at Room and Mild Temperature

Scheme 7.1 Mechanism for the Suzuki–Miyaura reaction.
Scheme 7.2 Lithiation/borylation/Suzuki–Miyaura cross-coupling sequence for the synthesis of biaryl derivatives.
Scheme 7.3 Lithiation/borylation/Suzuki–Miyaura cross-coupling sequence for the synthesis of biaryl derivatives in a microflow system.
Figure 7.1 Substrate scope of continuous flow lithiation/borylation/Suzuki–Miyaura cross-coupling sequence starting from aryl bromides. ^[a]The Suzuki–Miyaura cross-coupling reaction was finished in 4 min.
Scheme 7.4 Lithiation/borylation/Suzuki–Miyaura cross-coupling sequence of heteroarenes with aryl halides in a flow system.
Scheme 7.5 Substrate scope of continuous flow lithiation/borylation/Suzuki–Miyaura cross-coupling sequence starting from furan derivatives. ^[a]0.44 M NaF aqueous solution was used instead of KOH. ^[b]0.87 M KF aqueous solution was used instead of KOH.
Scheme 7.6 Total synthesis of diflunisal via lithiation/borylation/Suzuki–Miyaura cross-coupling in a microflow system.
Scheme 7.7 Continuous flow Suzuki–Miyaura cross-coupling sequence using SiliaCat DPP-Pd as supported catalyst.
Scheme 7.8 Substrate scope of continuous flow Suzuki–Miyaura cross-coupling sequence with different aryl bromides and 4-methoxyphenylboronic acid.
Scheme 7.9 Substrate scope of continuous flow Suzuki–Miyaura cross-coupling reaction with different aryl bromides/triflate and phenylboronic acid derivatives.
Scheme 7.10 Continuous flow Suzuki–Miyaura cross-coupling on a gram scale of substrate.
Scheme 7.11 Continuous flow Suzuki–Miyaura cross-coupling reaction of phenyl boronic acid with aryl halides using SS-Pd as heterogeneous catalyst.
Scheme 7.12 A schematic diagram of the Suzuki–Miyaura cross-coupling reaction of phenyl boronic acid with aryl halides using SS-Pd as heterogeneous catalyst.
Scheme 7.13 Mechanism of the Heck–Mizoroki reaction.
Scheme 7.14 Mechanism of the Heck–Matsuda reaction.
Scheme 7.15 Diazotization/palladium-catalyzed Heck–Matsuda coupling sequence.
Scheme 7.16 Continuous flow diazotization/homogeneous Heck–Matsuda cross-coupling sequence of aryl amines with methyl acrylate using a three-stream flow device.
Figure 7.2 Substrate scope of continuous flow diazotization/homogeneous Heck–Matsuda cross-coupling sequence starting from aniline derivatives. ^[a]Residence time for the diazotization in reactor 1.
Scheme 7.17 Continuous flow diazotization/heterogeneous Heck–Matsuda cross-coupling sequence of aryl amines with methyl acrylate using a three-stream flow device.
Figure 7.3 Substrate scope of continuous flow diazotization/heterogeneous Heck–Matsuda cross-coupling sequence starting from aniline derivatives. ^[a]Total residence time including reactors 1 and 2.
Scheme 7.18 Oxidative Heck coupling reaction between 4-methoxyphenyl boronic acid and ethyl acrylate.
Scheme 7.19 Continuous flow oxidative Heck cross-coupling sequence of aryl boronic acid with ethyl acrylate using a dual-channel microreactor.
Scheme 7.20 Substrate scope of continuous flow oxidative Heck cross-coupling reaction starting from aryl boronic acids.
Scheme 7.21 Mechanism for the Murahashi reaction.
Scheme 7.22 Lithiation/Murahashi cross-coupling sequence for the synthesis of biaryl derivatives in continuous flow.
Scheme 7.23 Continuous flow lithiation/Murahashi cross-coupling sequence of aryl bromides using a two-stream flow device.
Scheme 7.24 Substrate scope of continuous flow lithiation/Murahashi cross-coupling reaction starting from aryl boronic acids. ^[a]CPME was used as solvent in the presence of TMEDA (3 equiv.) for the Murahashi cross-coupling reaction.
Scheme 7.25 Continuous flow lithiation/Murahashi cross-coupling sequence starting from thiophene.

Chapter 8: Catalysis for Environmental Applications

Figure 8.1 Effect of Pd loading to ZVI immobilized onto activated carbon on 2-chlorobiphenyl (PCB) dechlorination kinetics.
Figure 8.2 (a) Graphene/TiO₂ and (b) graphene/ZnO nanohybrid films displaying the charge transfer mechanisms occurring during the photocatalytic process.
Figure 8.3 (a) Structure of a hybrid organolead halide perovskite. (Cai et al. 2013 [84]. Reproduced with permission of Royal Society of Chemistry.) (b) Image of flexible perovskite solar cell on PET/ITO substrate and (c) performance of flexible solar cell pre- and post-bending.
Figure 8.4 Scheme displaying the photocatalytic mechanism occurring within the Ag₃PO₄/g-C₃N₄ composite.

Case Study 1: Magnetic Pd Catalysts for Benzyl Alcohol Oxidation to Benzaldehyde

Figure 1 TEM images of (a) 1.0Pd/MagSBA, (b) 2.0Pd/MagSBA, (c) 3.0Pd/MagSBA, and (d) 4.0Pd/MagSBA, respectively.
Figure 2 XRD patterns of Pd/MagSBA.
Figure 3 Catalytic performance of 3.0Pd/MagSBA: (a) 80 °C, (b) 85 °C, and (c) 90 °C.
Figure 4 Catalytic performance of 2.0Pd/MagSBA: (a) 80 °C, (b) 85 °C, and (c) 90 °C.
Figure 5 Catalytic performance at 85 °C: (a) 4.0Pd/MagSBA, (b) 3.0Pd/MagSBA, (c) 2.0Pd/MagSBA, and (d) 1.0Pd/MagSBA.
Figure 6 Recycling ability of 3.0Pd/MagSBA.

Case Study 2: Development of Hydrothermally Stable Functional Materials for Sustainable Conversion of Biomass to Furan Compounds

Figure 1 Role of Lewis and Brønsted acids in mechanism of xylose dehydration [28].
Figure 2 Yield of furfural using various standard catalyst.
Figure 3 XRD patterns of (a) MIL-101(Cr) and (b) MIL-OTS.
Figure 4 FTIR spectra of MIL-101(Cr) and MIL-OTS.
Figure 5 TEM images of (a) MIL-101(Cr), (b) MIL-OTS-0.5, (c) STEM image of MIL-OTS-0.5, and (d–e) EDS Mapping of MIL-OTS-0.5.
Figure 6 XRD pattern of (a) raw fly ash and (b) AFA.
Figure 7 FTIR spectra of raw fly ash and AFA.
Figure 8 TEM-EDX of AFA showing uniform distribution of Si, Al, O, and S.
Figure 9 XRD patterns of (a) AFA, (b) MIL-101(Cr), and (c) MIL-AFA.
Figure 10 TEM image and EDS of MIL-AFA.
Figure 11 FTIR spectra of MIL-SnP-composite, mesoporous SnP and MIL-101(Cr).
Figure 12 ³¹P MAS NMR spectra of SnP and MIL-SnP.
Figure 13 TEM-EDS of MIL-SnP composite.
Figure 14 N₂ adsorption-desorption isotherms of catalysts developed.
Figure 15 FTIR-Pyridine spectra of catalysts developed.
Figure 16 TGA profile of catalysts developed.

List of Tables

Chapter 1: Introduction to Room-Temperature Catalysis

Table 1.1 Properties of crude and upgraded oil
Table 1.2 Reusability of the SiliaCat Pd(0) hydrogel in the selective catalytic hydrogenation of trans-cinnamic acid under mild conditions
Table 1.3 Comparison of the results obtained from Au NP@SIL-g-G with other supported Au catalysts for the oxidation of benzyl alcohol

Chapter 3: Heterogeneous Room Temperature Catalysis – Nanomaterials

Table 3.1 A list of nanomaterials for the room temperature catalytic reactions

Chapter 4: Biocatalysis at Room Temperature

Table 4.1 Examples of α-chiral amines and transaminases sources
Table 4.2 Subdivisions of hydrolases, according to http://www.enzyme-database.org
Table 4.3 Some applications of enzymes and ionic liquids for biocatalysis at room temperature
Table 4.4 Products and conversions (by HPLC) obtained from the transesterification reaction of soybean oil by Pseudomonas cepacia lipase (PS-Amano) with alcohols in BMI · NTf₂ at room temperature [209]

Sustainable Catalysis

Energy-Efficient Reactions and Applications

Edited by Rafael Luque and Frank Leung-Yuk Lam

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