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Search for "nanotube" in Full Text gives 18 result(s) in Beilstein Journal of Organic Chemistry.
Possible bi-stable structures of pyrenebutanoic acid-linked protein molecules adsorbed on graphene: theoretical study
- Yasuhiro Oishi,
- Motoharu Kitatani and
- Koichi Kusakabe
Beilstein J. Org. Chem. 2024, 20, 570–577, doi:10.3762/bjoc.20.49
- sensor chips and specifically binds to the antibody. The antigen is then detected by observing the change in the vibrational frequency before and after the injection of the antigen. The immobilization of a protein using a PASE linker on carbon nanotube [1], graphite [4], and graphene [5] has been
Graphical Abstract
Figure 1: (a) Molecular structure of 1-pyrenebutanoic acid succinimidyl ester (PASE). The black, white, red, ...
Figure 2: (a) Local structures around the butyl chain in conformation 1, the structure at activation barrier ...
Figure 3: Structure of PASE on graphene at the activation barrier top [9]. Detailed values of the torsion angle ...
Enhanced host–guest interaction between [10]cycloparaphenylene ([10]CPP) and [5]CPP by cationic charges
- Eiichi Kayahara,
- Yoshiyuki Mizuhata and
- Shigeru Yamago
Beilstein J. Org. Chem. 2024, 20, 436–444, doi:10.3762/bjoc.20.38
- Eiichi Kayahara Yoshiyuki Mizuhata Shigeru Yamago Institute for Chemical Research, Kyoto University, Uji 611-0011, Japan 10.3762/bjoc.20.38 Abstract A dication of [5]cycloparaphenylene ([5]CPP2+) was selectively encapsulated by neutral [10]CPP to form the shortest double-layer carbon nanotube
Graphical Abstract
Figure 1: Structures of a) [10]CPP⊃C60, (b) [n+5]CPP⊃[n]CPP, and (c) [10]CPP⊃[5]CPP2+ (this work).
Figure 2: 1H NMR spectra (CD2Cl2, 25 °C) of a) a mixture of [8]–[12]CPPs and [5]CPP2+[B(C6F5)4−]2 before and aft...
Figure 3: Cyclic voltammograms of [10]CPP⊃[5]CPP2+[B(C6F5)4−]2, [10]CPP, and [5]CPP2+[B(C6F5)4−]2 in Bu4N+ B(C...
Figure 4: UV–vis–NIR spectra of [10]CPP⊃[5]CPP2+[B(C6F5)4−]2 (black), [10]CPP (blue), and [5]CPP2+[B(C6F5)4−]2...
Figure 5: Top and side view of [10]CPP⊃[5]CPP2+ complexes a) 1, b) 2, and c) 3 obtained by DFT calculation at...
Figure 6: HOMO−1, HOMO, LUMO, and LUMO+1 orbitals of [10]CPP⊃[5]CPP2+ (1), [5]CPP2+, and [10]CPP.
Figure 7: X-ray crystal structure of [10]CPP⊃[5]CPP2+[B(C6F5)4]2. a) Side and b) top views of ORTEP drawings....
Green and sustainable approaches for the Friedel–Crafts reaction between aldehydes and indoles
- Periklis X. Kolagkis,
- Eirini M. Galathri and
- Christoforos G. Kokotos
Beilstein J. Org. Chem. 2024, 20, 379–426, doi:10.3762/bjoc.20.36
- conversion rate of the formed BIM product to 90–95%, compared to the 85–87% of the latter after 15 minutes of reflux. The nanotube catalyst was retrieved with a simple filtration, utilizing ethyl acetate and was reused for four synthetic cycles, before there was a decrease in catalytic activity, which was
- . immobilized carbon nanotubes on sulfonated polyacrylamide creating polymer/carbon nanotube composites, which could also be employed in the synthesis of BIMs [115][116]. This methodology used a catalyst loading of 5 mol % under reflux conditions (85 °C) in acetonitrile for 30–40 minutes with product yields
Graphical Abstract
Scheme 1: Examples of BIMs used for their medicinal properties.
Scheme 2: Mechanisms for the synthesis of BIMs using protic or Lewis acids as catalysts.
Scheme 3: Synthesis of bis(indolyl)methanes using DBDMH.
Scheme 4: Competition experiments and synthesis of bis(indolyl)methanes using DBDMH.
Scheme 5: Proposed mechanism for formation of BIM of using DBDMH.
Scheme 6: Synthesis of bis(indolyl)methanes using I2.
Scheme 7: General reaction mechanism upon halogen bonding.
Scheme 8: Synthesis of bis(indolyl)methanes using I2, introduced by Ji.
Scheme 9: Synthesis of bis(indolyl)methanes using Br2 in CH3CN.
Scheme 10: Βidentate halogen-bond donors.
Scheme 11: Synthesis of bis(indolyl)methanes using bidentate halogen-bond donor 26.
Scheme 12: Proposed reaction mechanism.
Scheme 13: Synthesis of bis(indolyl)methanes using iodoalkyne as catalyst.
Scheme 14: Proposed reaction mechanism.
Scheme 15: Optimized reaction conditions used by Ramshini.
Scheme 16: Activation of the carbonyl group by HPA/TPI-Fe3O4.
Scheme 17: Synthesis of BIMs in the presence of nanoAg-Pt/SiO2-doped silicate.
Scheme 18: Mechanism of action proposed by Khalafi-Nezhad et al.
Scheme 19: Activation of the carbonyl group by the Cu–isatin Schiff base complex.
Scheme 20: Optimum reaction conditions published by Jain.
Scheme 21: Organocatalytic protocol utilizing nanoparticles introduced by Bankar.
Scheme 22: Activation of the carbonyl group by the AlCl3·6H2O-SDS-SiO2 complex.
Scheme 23: Optimal reaction conditions for the aforementioned nano-Fe3O4 based catalysts.
Scheme 24: Nanocatalytic protocol proposed by Kaur et al.
Scheme 25: Microwave approach introduced by Yuan.
Scheme 26: Microwave approach introduced by Zahran et al.
Scheme 27: Microwave irradiation protocol introduced by Bindu.
Scheme 28: Silica-supported microwave irradiation protocol.
Scheme 29: Proposed mechanism for formation of BIM by Nongkhlaw.
Scheme 30: Microwave-assisted synthesis of BIMs catalyzed by succinic acid.
Scheme 31: Proposed mechanism of action of MMO-4.
Scheme 32: Catalytic approach introduced by Muhammadpoor-Baltork et al.
Scheme 33: Reaction conditions used by Xiao-Ming.
Scheme 34: Ultrasonic irradiation-based protocol published by Saeednia.
Scheme 35: Pyruvic acid-mediated synthesis of BIMs proposed by Thopate.
Scheme 36: Synthesis of BIMs using [bmim]BF4 or [bmim]PF6 ionic liquids.
Scheme 37: Synthesis of BIMs utilizing In(OTf)3 in octylmethylimidazolium hexafluorophosphate as ionic liquid.
Scheme 38: FeCl3·6H2O-catalyzed synthesis of BIMs with use of ionic liquid.
Scheme 39: Synthesis of BIMs utilizing the [hmim]HSO4/EtOH catalytic system.
Scheme 40: Synthesis of BIMs utilizing acidic ionic liquid immobilized on silica gel (ILIS-SO2Cl).
Scheme 41: The [bmim][MeSO4]-catalyzed reaction of indole with various aldehydes.
Scheme 42: The role of [bmim][MeSO4] in catalyzing the reaction of indole with aldehydes.
Scheme 43: Synthesis of BIMs utilizing FeCl3-based ionic liquid ([BTBAC]Cl-FeCl3) as catalyst.
Scheme 44: Synthesis of BIMs using [Msim]Cl at room temperature.
Scheme 45: [Et3NH][H2PO4]-catalyzed synthesis of bis(indolyl)methanes.
Scheme 46: PILs-catalyzed synthesis of bis(indolyl)methanes.
Scheme 47: FSILs-mediated synthesis of bis(indolyl)methanes.
Scheme 48: Possible “release and catch” catalytic process.
Scheme 49: Synthesis of bis(indolyl)methanes by [DABCO-H][HSO4].
Scheme 50: Synthesis of bis(indolyl)methanes by [(THA)(SO4)].
Scheme 51: Synthesis of BBSI-Cl and BBSI-HSO4.
Scheme 52: Synthesis of BIMs in the presence of BBSI-Cl and BBSI-HSO4.
Scheme 53: Chemoselectivity of the present method.
Scheme 54: Synthesis of BIMs catalyzed by chitosan-supported ionic liquid.
Scheme 55: Proposed mechanism of action of CSIL.
Scheme 56: Optimization of the reaction in DESs.
Scheme 57: Synthesis of BIMs using ChCl/SnCl2 as DES.
Scheme 58: Synthesis of BIMs derivatives in presence of DES.
Scheme 59: BIMs synthesis in choline chloride/urea (CC/U).
Scheme 60: Flow chemistry-based synthesis of BIMs by Ley.
Scheme 61: Flow chemistry-based synthesis of BIMs proposed by Nam et al.
Scheme 62: Amino-catalyzed reaction of indole with propionaldehyde.
Scheme 63: Aminocatalytic synthesis of BIMs.
Scheme 64: Proposed mechanism for the aminocatalytic synthesis of BIMs.
Scheme 65: Enzymatic reaction of indole with aldehydes.
Scheme 66: Proposed mechanism for the synthesis of BIMs catalyzed by TLIM.
Scheme 67: Proposed reaction mechanism by Badsara.
Scheme 68: Mechanism proposed by D’Auria.
Scheme 69: Photoinduced thiourea catalysis.
Scheme 70: Proposed mechanism of photoacid activation.
Scheme 71: Proposed mechanism of action for CF3SO2Na.
Scheme 72: Proposed mechanism for the synthesis of BIMs by Mandawad.
Scheme 73: Proposed mechanism for the (a) acid generation and (b) synthesis of BIMs.
Scheme 74: a) Reaction conditions employed by Khaksar and b) activation of the carbonyl group by HFIP.
Scheme 75: Activation of the carbonyl group by the PPy@CH2Br through the formation of a halogen bond.
Scheme 76: Reaction conditions utilized by Mhaldar et al.
Scheme 77: a) Reaction conditions employed by López and b) activation of the carbonyl group by thiourea.
Scheme 78: Infrared irradiation approach introduced by Luna-Mora and his research group.
Scheme 79: Synthesis of BIMs with the use of the Fe–Zn BMOF.
Electron-beam-promoted fullerene dimerization in nanotubes: insights from DFT computations
- Laura Abella,
- Gerard Novell-Leruth,
- Josep M. Ricart,
- Josep M. Poblet and
- Antonio Rodríguez-Fortea
Beilstein J. Org. Chem. 2024, 20, 92–100, doi:10.3762/bjoc.20.10
- have been published that record the dynamic behavior of a wide range of molecules and chemical reactions. One such process was the dimerization of C60 fullerene in a carbon nanotube peapod, i.e., hybrid structures consisting of fullerene molecules encapsulated in single-walled carbon nanotubes (SWCNT
- the reaction either via singlet excitation or via radical cation formation (Scheme 1). Estimation of the activation barrier for the [2 + 2] cycloaddition when the nanotube acts as a sensitizer is 33.5 ± 6.8 kJ mol−1. This value agrees with computational predictions for the reaction via an excited
- analyzed the interaction between C60 and the nanotube within the peapod. Next, we have found that some dimeric C60–C60 fullerene structures inside the carbon nanotube are thermodynamically favorable. Experiments indicate that, besides C60 sensitization via a singlet excited state, the [2 + 2] cycloaddition
Graphical Abstract
Scheme 1: Proposed radical cation mechanism for the dimerization of two C60 cages inside a metallic carbon na...
Figure 1: DFT-optimized structures of C60 dimers 1-D2h, 1-Cs and nanotubular C120-NT-D5d fullerene.
Figure 2: Energy profiles for the dimerization of 2 C60 and C60 + C60•+ fullerenes in the gas phase. All ener...
Figure 3: Energy profiles for the dimerization of 2 C60 (neutral) and C60 + C60•+ (radical cation) fullerenes...
Figure 4: Proposed sequence of C60 dimers up to the formation of dimer HPR-Cs•+.
Preparing a liquid crystalline dispersion of carbon nanotubes with high aspect ratio
- Keiko Kojima,
- Nodoka Kosugi,
- Hirokuni Jintoku,
- Kazufumi Kobashi and
- Toshiya Okazaki
Beilstein J. Org. Chem. 2024, 20, 52–58, doi:10.3762/bjoc.20.7
- 305-8571, Japan 10.3762/bjoc.20.7 Abstract We successfully prepared a surfactant-assisted carbon nanotube (CNT) liquid crystal (LC) dispersion with double-walled CNTs (DWCNTs) having a high aspect ratio (≈1378). Compared to dispersions of single-walled CNTs (SWCNTs) with lower aspect ratio, the
- . Keywords: aqueous dispersion; bar-coating; carbon nanotube; coffee-ring effect; liquid crystal; Introduction Carbon nanotubes (CNTs) are cylindrical carbon structures with high electrical conductivity and tensile strength in the direction of the tube, anticipated as durable and highly conductive fibers
- carbon nanotube dispersions with high aspect ratios, we utilized DWCNTs obtained from Shenzhen Nanotech Port Co. Ltd. Supporting Information File 1 provides characterization details. Briefly, the Raman G/D ratio was approximately 37 (Supporting Information File 1, Figure S1d), indicating high
Graphical Abstract
Figure 1: (a) Size distribution of DWCNTs in dispersion by DCS measurements. (b) Optical microscopy image of ...
Figure 2: (a) Phase diagram of the DWCNT dispersion. The nematic phase, biphasic state and isotropic phase ar...
Figure 3: Observed tactoid aspect ratio R/r as a function of tactoid volume Rr2. Filled circle and open circl...
Figure 4: (a, b) POM images of the DWCNT film at (a) 0° and (b) 45° under crossed polarizers (white double ar...
Figure 5: (a) Photograph of the DWCNT film. Thicknesses were measured at 7 spots along the yellow dashed line...
Anion–π catalysis on carbon allotropes
- M. Ángeles Gutiérrez López,
- Mei-Ling Tan,
- Giacomo Renno,
- Augustina Jozeliūnaitė,
- J. Jonathan Nué-Martinez,
- Javier Lopez-Andarias,
- Naomi Sakai and
- Stefan Matile
Beilstein J. Org. Chem. 2023, 19, 1881–1894, doi:10.3762/bjoc.19.140
- NDI surfaces to the nanotube to increase intrinsic anion–π interactions with the highest polarizability. For interfacing with CNTs, the π-basic pyrenes rather than the π-acidic NDIs are most popular [82][88][90][96][97][98][99]. Equipped with a tertiary amine, the catalytic activity of dyad 63
Graphical Abstract
Figure 1: (A) Anion–π catalysis: Stabilization of anionic transition states from substrate S to product P on ...
Figure 2: Bioinspired enolate addition chemistry to benchmark anion–π catalysts: Stabilization of “enol” inte...
Figure 3: Structure and activity of fullerene-amine dyads to catalyze the intrinsically disfavored but biolog...
Figure 4: Asymmetric anion–π catalysis of intrinsically disfavored exo-selective Diels–Alder reactions on ful...
Figure 5: Asymmetric anion–π catalysis to install remote stereogenic centers on fullerene catalyst 21, with n...
Figure 6: Primary anion–π autocatalysis on monofunctional fullerene 31, with catalytic and autocatalytic rate...
Figure 7: (A) Macrodipoles induced by anionic transition states account for anion–π catalysis on fullerenes. ...
Figure 8: Structure and activity of covalently and non-covalently modified SWCNTs and MWCNTs, with A/D ratios...
Figure 9: (A) Epoxide-opening ether cyclization on pristine carbon nanotubes occurs with (XVI) but not withou...
Figure 10: Electric-field-induced anion–π catalysis on MWCNTs 3 on graphite 76 in electrochemical microfluidic...
A comprehensive review of flow chemistry techniques tailored to the flavours and fragrances industries
- Guido Gambacorta,
- James S. Sharley and
- Ian R. Baxendale
Beilstein J. Org. Chem. 2021, 17, 1181–1312, doi:10.3762/bjoc.17.90
Graphical Abstract
Figure 1: Representative shares of the global F&F market (2018) segmented on their applications [1].
Figure 2: General structure of an international fragrance company [2].
Figure 3: The Michael Edwards fragrance wheel.
Figure 4: Examples of oriental (1–3), woody (4–7), fresh (8–10), and floral (11 and 12) notes.
Figure 5: A basic depiction of batch vs flow.
Scheme 1: Examples of reactions for which flow processing outperforms batch.
Scheme 2: Some industrially important aldol-based transformations.
Scheme 3: Biphasic continuous aldol reactions of acetone and various aldehydes.
Scheme 4: Aldol synthesis of 43 in flow using LiHMDS as the base.
Scheme 5: A semi-continuous synthesis of doravirine (49) involving a key aldol reaction.
Scheme 6: Enantioselective aldol reaction using 5-(pyrrolidin-2-yl)tetrazole (51) as catalyst in a microreact...
Scheme 7: Gröger's example of asymmetric aldol reaction in aqueous media.
Figure 6: Immobilised reagent column reactor types.
Scheme 8: Photoinduced thiol–ene coupling preparation of silica-supported 5-(pyrrolidin-2-yl)tetrazole 63 and...
Scheme 9: Continuous-flow approach for enantioselective aldol reactions using the supported catalyst 67.
Scheme 10: Ötvös’ employment of a solid-supported peptide aldol catalyst in flow.
Scheme 11: The use of proline tetrazole packed in a column for aldol reaction between cyclohexanone (65) and 2...
Scheme 12: Schematic diagram of an aminosilane-grafted Si-Zr-Ti/PAI-HF reactor for continuous-flow aldol and n...
Scheme 13: Continuous-flow condensation for the synthesis of the intermediate 76 to nabumetone (77) and Microi...
Scheme 14: Synthesis of ψ-Ionone (80) in continuous-flow via aldol condensation between citral (79) and aceton...
Scheme 15: Synthesis of β-methyl-ionones (83) from citral (79) in flow. The steps are separately described, an...
Scheme 16: Continuous-flow synthesis of 85 from 84 described by Gavriilidis et al.
Scheme 17: Continuous-flow scCO2 apparatus for the synthesis of 2-methylpentanal (87) and the self-condensed u...
Scheme 18: Chen’s two-step flow synthesis of coumarin (90).
Scheme 19: Pechmann condensation for the synthesis of 7-hydroxyxcoumarin (93) in flow. The setup extended to c...
Scheme 20: Synthesis of the dihydrojasmonate 35 exploiting nitro derivative proposed by Ballini et al.
Scheme 21: Silica-supported amines as heterogeneous catalyst for nitroaldol condensation in flow.
Scheme 22: Flow apparatus for the nitroaldol condensation of p-hydroxybenzaldehyde (102) to nitrostyrene 103 a...
Scheme 23: Nitroaldol reaction of 64 to 105 employing a quaternary ammonium functionalised PANF.
Scheme 24: Enantioselective nitroaldol condensation for the synthesis of 108 under flow conditions.
Scheme 25: Enatioselective synthesis of 1,2-aminoalcohol 110 via a copper-catalysed nitroaldol condensation.
Scheme 26: Examples of Knoevenagel condensations applied for fragrance components.
Scheme 27: Flow apparatus for Knoevenagel condensation described in 1989 by Venturello et al.
Scheme 28: Knoevenagel reaction using a coated multichannel membrane microreactor.
Scheme 29: Continuous-flow apparatus for Knoevenagel condensation employing sugar cane bagasse as support deve...
Scheme 30: Knoevenagel reaction for the synthesis of 131–135 in flow using an amine-functionalised silica gel. ...
Scheme 31: Continuous-flow synthesis of compound 137, a key intermediate for the synthesis of pregabalin (138)...
Scheme 32: Continuous solvent-free apparatus applied for the synthesis of compounds 140–143 using a TSE. Throu...
Scheme 33: Lewis et al. developed a spinning disc reactor for Darzens condensation of 144 and a ketone to furn...
Scheme 34: Some key industrial applications of conjugate additions in the F&F industry.
Scheme 35: Continuous-flow synthesis of 4-(2-hydroxyethyl)thiomorpholine 1,1-dioxide (156) via double conjugat...
Scheme 36: Continuous-flow system for Michael addition using CsF on alumina as the catalyst.
Scheme 37: Calcium chloride-catalysed asymmetric Michael addition using an immobilised chiral ligand.
Scheme 38: Continuous multistep synthesis for the preparation of (R)-rolipram (173). Si-NH2: primary amine-fun...
Scheme 39: Continuous-flow Michael addition using ion exchange resin Amberlyst® A26.
Scheme 40: Preparation of the heterogeneous catalyst 181 developed by Paixão et al. exploiting Ugi multicompon...
Scheme 41: Continuous-flow system developed by the Paixão’s group for the preparation of Michael asymmetric ad...
Scheme 42: Continuous-flow synthesis of nitroaldols catalysed by supported catalyst 184 developed by Wennemers...
Scheme 43: Heterogenous polystyrene-supported catalysts developed by Pericàs and co-workers.
Scheme 44: PANF-supported pyrrolidine catalyst for the conjugate addition of cyclohexanone (65) and trans-β-ni...
Scheme 45: Synthesis of (−)-paroxetine precursor 195 developed by Ötvös, Pericàs, and Kappe.
Scheme 46: Continuous-flow approach for the 5-step synthesis of (−)-oseltamivir (201) as devised by Hayashi an...
Scheme 47: Continuous-flow enzyme-catalysed Michael addition.
Scheme 48: Continuous-flow copper-catalysed 1,4 conjugate addition of Grignard reagents to enones. Reprinted w...
Scheme 49: A collection of commonly encountered hydrogenation reactions.
Figure 7: The ThalesNano H-Cube® continuous-flow hydrogenator.
Scheme 50: Chemoselective reduction of an α,β-unsaturated ketone using the H-Cube® reactor.
Scheme 51: Incorporation of Lindlar’s catalyst into the H-Cube® reactor for the reduction of an alkyne.
Scheme 52: Continuous-flow semi-hydrogenation of alkyne 208 to 209 using SACs with H-Cube® system.
Figure 8: The standard setups for tube-in-tube gas–liquid reactor units.
Scheme 53: Homogeneous hydrogenation of olefins using a tube-in-tube reactor setup.
Scheme 54: Recyclable heterogeneous flow hydrogenation system.
Scheme 55: Leadbeater’s reverse tube-in-tube hydrogenation system for olefin reductions.
Scheme 56: a) Hydrogenation using a Pd-immobilised microchannel reactor (MCR) and b) a representation of the i...
Scheme 57: Hydrogenation of alkyne 238 exploiting segmented flow in a Pd-immobilised capillary reactor.
Scheme 58: Continuous hydrogenation system for the preparation of cyrene (241) from (−)-levoglucosenone (240).
Scheme 59: Continuous hydrogenation system based on CSMs developed by Hornung et al.
Scheme 60: Chemoselective reduction of carbonyls (ketones over aldehydes) in flow.
Scheme 61: Continuous system for the semi-hydrogenation of 256 and 258, developed by Galarneau et al.
Scheme 62: Continuous synthesis of biodiesel fuel 261 from lignin-derived furfural acetone (260).
Scheme 63: Continuous synthesis of γ-valerolacetone (263) via CTH developed by Pineda et al.
Scheme 64: Continuous hydrogenation of lignin-derived biomass (products 265, 266, and 267) using a sustainable...
Scheme 65: Ru/C or Rh/C-catalysed hydrogenation of arene in flow as developed by Sajiki et al.
Scheme 66: Polysilane-immobilized Rh–Pt-catalysed hydrogenation of arenes in flow by Kobayashi et al.
Scheme 67: High-pressure in-line mixing of H2 for the asymmetric reduction of 278 at pilot scale with a 73 L p...
Figure 9: Picture of the PFR employed at Eli Lilly & Co. for the continuous hydrogenation of 278 [287]. Reprinted ...
Scheme 68: Continuous-flow asymmetric hydrogenation using Oppolzer's sultam 280 as chiral auxiliary.
Scheme 69: Some examples of industrially important oxidation reactions in the F&F industry. CFL: compact fluor...
Scheme 70: Gold-catalysed heterogeneous oxidation of alcohols in flow.
Scheme 71: Uozumi’s ARP-Pt flow oxidation protocol.
Scheme 72: High-throughput screening of aldehyde oxidation in flow using an in-line GC.
Scheme 73: Permanganate-mediated Nef oxidation of nitroalkanes in flow with the use of in-line sonication to p...
Scheme 74: Continuous-flow aerobic anti-Markovnikov Wacker oxidation.
Scheme 75: Continuous-flow oxidation of 2-benzylpyridine (312) using air as the oxidant.
Scheme 76: Continuous-flow photo-oxygenation of monoterpenes.
Scheme 77: A tubular reactor design for flow photo-oxygenation.
Scheme 78: Glucose oxidase (GOx)-mediated continuous oxidation of glucose using compressed air and the FFMR re...
Scheme 79: Schematic continuous-flow sodium hypochlorite/TEMPO oxidation of alcohols.
Scheme 80: Oxidation using immobilised TEMPO (344) was developed by McQuade et al.
Scheme 81: General protocol for the bleach/catalytic TBAB oxidation of aldehydes and alcohols.
Scheme 82: Continuous-flow PTC-assisted oxidation using hydrogen peroxide. The process was easily scaled up by...
Scheme 83: Continuous-flow epoxidation of cyclohexene (348) and in situ preparation of m-CPBA.
Scheme 84: Continuous-flow epoxidation using DMDO as oxidant.
Scheme 85: Mukayama aerobic epoxidation optimised in flow mode by the Favre-Réguillon group.
Scheme 86: Continuous-flow asymmetric epoxidation of derivatives of 359 exploiting a biomimetic iron catalyst.
Scheme 87: Continuous-flow enzymatic epoxidation of alkenes developed by Watts et al.
Scheme 88: Engineered multichannel microreactor for continuous-flow ozonolysis of 366.
Scheme 89: Continuous-flow synthesis of the vitamin D precursor 368 using multichannel microreactors. MFC: mas...
Scheme 90: Continuous ozonolysis setup used by Kappe et al. for the synthesis of various substrates employing ...
Scheme 91: Continuous-flow apparatus for ozonolysis as developed by Ley et al.
Scheme 92: Continuous-flow ozonolysis for synthesis of vanillin (2) using a film-shear flow reactor.
Scheme 93: Examples of preparative methods for ajoene (386) and allicin (388).
Scheme 94: Continuous-flow oxidation of thioanisole (389) using styrene-based polymer-supported peroxytungstat...
Scheme 95: Continuous oxidation of thiosulfinates using Oxone®-packed reactor.
Scheme 96: Continuous-flow electrochemical oxidation of thioethers.
Scheme 97: Continuous-flow oxidation of 400 to cinnamophenone (235).
Scheme 98: Continuous-flow synthesis of dehydrated material 401 via oxidation of methyl dihydrojasmonate (33).
Scheme 99: Some industrially important transformations involving Grignard reagents.
Scheme 100: Grachev et al. apparatus for continuous preparation of Grignard reagents.
Scheme 101: Example of fluidized Mg bed reactor with NMR spectrometer as on-line monitoring system.
Scheme 102: Continuous-flow synthesis of Grignard reagents and subsequent quenching reaction.
Figure 10: Membrane-based, liquid–liquid separator with integrated pressure control [52]. Adapted with permission ...
Scheme 103: Continuous-flow synthesis of 458, an intermediate to fluconazole (459).
Scheme 104: Continuous-flow synthesis of ketones starting from benzoyl chlorides.
Scheme 105: A Grignard alkylation combining CSTR and PFR technologies with in-line infrared reaction monitoring....
Scheme 106: Continuous-flow preparation of 469 from Grignard addition of methylmagnesium bromide.
Scheme 107: Continuous-flow synthesis of Grignard reagents 471.
Scheme 108: Preparation of the Grignard reagent 471 using CSTR and the continuous process for synthesis of the ...
Scheme 109: Continuous process for carboxylation of Grignard reagents in flow using tube-in-tube technology.
Scheme 110: Continuous synthesis of propargylic alcohols via ethynyl-Grignard reagent.
Scheme 111: Silica-supported catalysed enantioselective arylation of aldehydes using Grignard reagents in flow ...
Scheme 112: Acid-catalysed rearrangement of citral and dehydrolinalool derivatives.
Scheme 113: Continuous stilbene isomerisation with continuous recycling of photoredox catalyst.
Scheme 114: Continuous-flow synthesis of compound 494 as developed by Ley et al.
Scheme 115: Selected industrial applications of DA reaction.
Scheme 116: Multistep flow synthesis of the spirocyclic structure 505 via employing DA cycloaddition.
Scheme 117: Continuous-flow DA reaction developed in a plater flow reactor for the preparation of the adduct 508...
Scheme 118: Continuous-flow DA reaction using a silica-supported imidazolidinone organocatalyst.
Scheme 119: Batch vs flow for the DA reaction of (cyclohexa-1,5-dien-1-yloxy)trimethylsilane (513) with acrylon...
Scheme 120: Continuous-flow DA reaction between 510 and 515 using a shell-core droplet system.
Scheme 121: Continuous-flow synthesis of bicyclic systems from benzyne precursors.
Scheme 122: Continuous-flow synthesis of bicyclic scaffolds 527 and 528 for further development of potential ph...
Scheme 123: Continuous-flow inverse-electron hetero-DA reaction to pyridine derivatives such as 531.
Scheme 124: Comparison between batch and flow for the synthesis of pyrimidinones 532–536 via retro-DA reaction ...
Scheme 125: Continuous-flow coupled with ultrasonic system for preparation of ʟ-ascorbic acid derivatives 539 d...
Scheme 126: Two-step continuous-flow synthesis of triazole 543.
Scheme 127: Continuous-flow preparation of triazoles via CuAAC employing 546-based heterogeneous catalyst.
Scheme 128: Continuous-flow synthesis of compounds 558 through A3-coupling and 560 via AgAAC both employing the...
Scheme 129: Continuous-flow photoinduced [2 + 2] cycloaddition for the preparation of bicyclic derivatives of 5...
Scheme 130: Continuous-flow [2 + 2] and [5 + 2] cycloaddition on large scale employing a flow reactor developed...
Scheme 131: Continuous-flow preparation of the tricyclic structures 573 and 574 starting from pyrrole 570 via [...
Scheme 132: Continuous-flow [2 + 2] photocyclization of cinnamates.
Scheme 133: Continuous-flow preparation of cyclobutane 580 on a 5-plates photoreactor.
Scheme 134: Continuous-flow [2 + 2] photocycloaddition under white LED lamp using heterogeneous PCN as photocat...
Figure 11: Picture of the parallel tube flow reactor (PTFR) "The Firefly" developed by Booker-Milburn et al. a...
Scheme 135: Continuous-flow acid-catalysed [2 + 2] cycloaddition between silyl enol ethers and acrylic esters.
Scheme 136: Continuous synthesis of lactam 602 using glass column reactors.
Scheme 137: In situ generation of ketenes for the Staudinger lactam synthesis developed by Ley and Hafner.
Scheme 138: Application of [2 + 2 + 2] cycloadditions in flow employed by Ley et al.
Scheme 139: Examples of FC reactions applied in F&F industry.
Scheme 140: Continuous-flow synthesis of ibuprofen developed by McQuade et al.
Scheme 141: The FC acylation step of Jamison’s three-step ibuprofen synthesis.
Scheme 142: Synthesis of naphthalene derivative 629 via FC acylation in microreactors.
Scheme 143: Flow system for rapid screening of catalysts and reaction conditions developed by Weber et al.
Scheme 144: Continuous-flow system developed by Buorne, Muller et al. for DSD optimisation of the FC acylation ...
Scheme 145: Continuous-flow FC acylation of alkynes to yield β-chlorovinyl ketones such as 638.
Scheme 146: Continuous-flow synthesis of tonalide (619) developed by Wang et al.
Scheme 147: Continuous-flow preparation of acylated arene such as 290 employing Zr4+-β-zeolite developed by Kob...
Scheme 148: Flow system applied on an Aza-FC reaction catalysed by the thiourea catalyst 648.
Scheme 149: Continuous hydroformylation in scCO2.
Scheme 150: Two-step flow synthesis of aldehyde 655 through a sequential Heck reaction and subsequent hydroform...
Scheme 151: Single-droplet (above) and continuous (below) flow reactors developed by Abolhasani et al. for the ...
Scheme 152: Continuous hydroformylation of 1-dodecene (655) using a PFR-CSTR system developed by Sundmacher et ...
Scheme 153: Continuous-flow synthesis of the aldehyde 660 developed by Eli Lilly & Co. [32]. Adapted with permissio...
Scheme 154: Continuous asymmetric hydroformylation employing heterogenous catalst supported on carbon-based sup...
Scheme 155: Examples of acetylation in F&F industry: synthesis of bornyl (S,R,S-664) and isobornyl (S,S,S-664) ...
Scheme 156: Continuous-flow preparation of bornyl acetate (S,R,S-664) employing the oscillating flow reactor.
Scheme 157: Continuous-flow synthesis of geranyl acetate (666) from acetylation of geraniol (343) developed by ...
Scheme 158: 12-Ttungstosilicic acid-supported silica monolith-catalysed acetylation in flow.
Scheme 159: Continuous-flow preparation of cyclopentenone 676.
Scheme 160: Two-stage synthesis of coumarin (90) via acetylation of salicylaldehyde (88).
Scheme 161: Intensification process for acetylation of 5-methoxytryptamine (677) to melatonin (678) developed b...
Scheme 162: Examples of macrocyclic musky odorants both natural (679–681) and synthetic (682 and 683).
Scheme 163: Flow setup combined with microwave for the synthesis of macrocycle 686 via RCM.
Scheme 164: Continuous synthesis of 2,5-dihydro-1H-pyrroles via ring-closing metathesis.
Scheme 165: Continuous-flow metathesis of 485 developed by Leadbeater et al.
Figure 12: Comparison between RCM performed using different routes for the preparation of 696. On the left the...
Scheme 166: Continuous-flow RCM of 697 employed the solid-supported catalyst 698 developed by Grela, Kirschning...
Scheme 167: Continuous-flow RORCM of cyclooctene employing the silica-absorbed catalyst 700.
Scheme 168: Continuous-flow self-metathesis of methyl oleate (703) employing SILP catalyst 704.
Scheme 169: Flow apparatus for the RCM of 697 using a nanofiltration membrane for the recovery and reuse of the...
Scheme 170: Comparison of loadings between RCMs performed with different routes for the synthesis of 709.
Valorisation of plastic waste via metal-catalysed depolymerisation
- Francesca Liguori,
- Carmen Moreno-Marrodán and
- Pierluigi Barbaro
Beilstein J. Org. Chem. 2021, 17, 589–621, doi:10.3762/bjoc.17.53
- reused over four cycles with no efficiency decay. Similar effects were reported for Zn-substituted titanate nanotube (TiNT) catalysts [212][213]. Therein, a positive role of Zn2+ Lewis acid sites was demonstrated by the higher efficiency compared to the Na+ catalyst counterpart (Table 3, entry 2 vs entry
Graphical Abstract
Figure 1: Potential classification of plastic recycling processes. The area covered by the present review is ...
Figure 2: EG produced during glycolytic depolymerisation of PET using DEG + DPG as solvent and titanium(IV) n...
Scheme 1: Simplified representation of the conversion of 1,4-PBD to C16–C44 macrocycles using Ru metathesis c...
Figure 3: Main added-value monomers obtainable by catalytic depolymerisation of PET via chemolytic methods.
Scheme 2: Hydrogenolytic depolymerisation of PET by ruthenium complexes.
Scheme 3: Depolymerisation of PET via catalytic hydrosilylation by Ir(III) pincer complex.
Scheme 4: Catalytic hydrolysis (top) and methanolysis (bottom) reactions of PET.
Scheme 5: Depolymerisation of PET by glycolysis with ethylene glycol.
Figure 4: Glycolysis of PET: evolution of BHET yield over time, with and without zinc acetate catalyst (196 °...
Scheme 6: Potential activated complex for the glycolysis reaction of PET catalysed by metallated ILs and evol...
Scheme 7: One-pot, two-step process for PET repurposing via chemical recycling.
Scheme 8: Synthetic routes to PLA.
Scheme 9: Structures of the zinc molecular catalysts used for PLA-methanolysis in various works. a) See [265], b) ...
Scheme 10: Depolymerisation of PLLA by Zn–N-heterocyclic carbene complex.
Scheme 11: Salalen ligands.
Scheme 12: Catalytic hydrogenolysis of PLA.
Scheme 13: Catalytic hydrosilylation of PLA.
Scheme 14: Hydrogenative depolymerisation of PBT and PCL by molecular Ru catalysts.
Scheme 15: Glycolysis reaction of PCT by diethylene glycol.
Scheme 16: Polymerisation–depolymerisation cycle of 3,4-T6GBL.
Scheme 17: Polymerisation–depolymerisation cycle of 2,3-HDB.
Scheme 18: Hydrogenative depolymerisation of PBPAC by molecular Ru catalysts.
Scheme 19: Catalytic hydrolysis (top), alcoholysis (middle) and aminolysis (bottom) reactions of PBPAC.
Scheme 20: Hydrogenative depolymerisation of PPC (top) and PEC (bottom) by molecular Ru catalysts.
Scheme 21: Polymerisation-depolymerisation cycle of BEP.
Scheme 22: Hydrogenolysis of polyamides using soluble Ru catalysts.
Scheme 23: Catalytic depolymerisation of epoxy resin/carbon fibres composite.
Scheme 24: Depolymerisation of polyethers with metal salt catalysts and acyl chlorides.
Scheme 25: Proposed mechanism for the iron-catalysed depolymerisation reaction of polyethers. Adapted with per...
Recent advances on the transition-metal-catalyzed synthesis of imidazopyridines: an updated coverage
- Gagandeep Kour Reen,
- Ashok Kumar and
- Pratibha Sharma
Beilstein J. Org. Chem. 2019, 15, 1612–1704, doi:10.3762/bjoc.15.165
Graphical Abstract
Figure 1: Various drugs having IP nucleus.
Figure 2: Participation percentage of various TMs for the syntheses of IPs.
Scheme 1: CuI–NaHSO4·SiO2-catalyzed synthesis of imidazo[1,2-a]pyridines.
Scheme 2: Experimental examination of reaction conditions.
Scheme 3: One-pot tandem reaction for the synthesis of 2-haloimidazopyridines.
Scheme 4: Mechanistic scheme for the synthesis of 2-haloimidazopyridine.
Scheme 5: Copper-MOF-catalyzed three-component reaction (3-CR) for imidazo[1,2-a]pyridines.
Scheme 6: Mechanism for copper-MOF-driven synthesis.
Scheme 7: Heterogeneous synthesis via titania-supported CuCl2.
Scheme 8: Mechanism involving oxidative C–H functionalization.
Scheme 9: Heterogeneous synthesis of IPs.
Scheme 10: One-pot regiospecific synthesis of imidazo[1,2-a]pyridines.
Scheme 11: Vinyl azide as an unprecedented substrate for imidazo[1,2-a]pyridines.
Scheme 12: Radical pathway.
Scheme 13: Cu(I)-catalyzed transannulation approach for imidazo[1,5-a]pyridines.
Scheme 14: Plausible radical pathway for the synthesis of imidazo[1,5-a]pyridines.
Scheme 15: A solvent-free domino reaction for imidazo[1,2-a]pyridines.
Scheme 16: Cu-NPs-mediated synthesis of imidazo[1,2-a]pyridines.
Scheme 17: CuI-catalyzed synthesis of isoxazolylimidazo[1,2-a]pyridines.
Scheme 18: Functionalization of 4-bromo derivative via Sonogashira coupling reaction.
Scheme 19: A plausible reaction pathway.
Scheme 20: Cu(I)-catalyzed intramolecular oxidative C–H amidation reaction.
Scheme 21: One-pot synthetic reaction for imidazo[1,2-a]pyridine.
Scheme 22: Plausible reaction mechanism.
Scheme 23: Cu(OAc)2-promoted synthesis of imidazo[1,2-a]pyridines.
Scheme 24: Mechanism for aminomethylation/cycloisomerization of propiolates with imines.
Scheme 25: Three-component synthesis of imidazo[1,2-a]pyridines.
Figure 3: Scope of pyridin-2(1H)-ones and acetophenones.
Scheme 26: CuO NPS-promoted A3 coupling reaction.
Scheme 27: Cu(II)-catalyzed C–N bond formation reaction.
Scheme 28: Mechanism involving Chan–Lam/Ullmann coupling.
Scheme 29: Synthesis of formyl-substituted imidazo[1,2-a]pyridines.
Scheme 30: A tandem sp3 C–H amination reaction.
Scheme 31: Probable mechanistic approach.
Scheme 32: Dual catalytic system for imidazo[1,2-a]pyridines.
Scheme 33: Tentative mechanism.
Scheme 34: CuO/CuAl2O4/ᴅ-glucose-promoted 3-CCR.
Scheme 35: A tandem CuOx/OMS-2-based synthetic strategy.
Figure 4: Biomimetic catalytic oxidation in the presence of electron-transfer mediators (ETMs).
Scheme 36: Control experiment.
Scheme 37: Copper-catalyzed C(sp3)–H aminatin reaction.
Scheme 38: Reaction of secondary amines.
Scheme 39: Probable mechanistic pathway.
Scheme 40: Coupling reaction of α-azidoketones.
Scheme 41: Probable pathway.
Scheme 42: Probable mechanism with free energy calculations.
Scheme 43: MCR for cyanated IP synthesis.
Scheme 44: Substrate scope for the reaction.
Scheme 45: Reaction mechanism.
Scheme 46: Probable mechanistic pathway for Cu/ZnAl2O4-catalyzed reaction.
Scheme 47: Copper-catalyzed double oxidative C–H amination reaction.
Scheme 48: Application towards different coupling reactions.
Scheme 49: Reaction mechanism.
Scheme 50: Condensation–cyclization approach for the synthesis of 1,3-diarylated imidazo[1,5-a]pyridines.
Scheme 51: Optimized reaction conditions.
Scheme 52: One-pot 2-CR.
Scheme 53: One-pot 3-CR without the isolation of chalcone.
Scheme 54: Copper–Pybox-catalyzed cyclization reaction.
Scheme 55: Mechanistic pathway catalyzed by Cu–Pybox complex.
Scheme 56: Cu(II)-promoted C(sp3)-H amination reaction.
Scheme 57: Wider substrate applicability for the reaction.
Scheme 58: Plausible reaction mechanism.
Scheme 59: CuI assisted C–N cross-coupling reaction.
Scheme 60: Probable reaction mechanism involving sp3 C–H amination.
Scheme 61: One-pot MCR-catalyzed by CoFe2O4/CNT-Cu.
Scheme 62: Mechanistic pathway.
Scheme 63: Synthetic scheme for 3-nitroimidazo[1,2-a]pyridines.
Scheme 64: Plausible mechanism for CuBr-catalyzed reaction.
Scheme 65: Regioselective synthesis of halo-substituted imidazo[1,2-a]pyridines.
Scheme 66: Synthesis of 2-phenylimidazo[1,2-a]pyridines.
Scheme 67: Synthesis of diarylated compounds.
Scheme 68: CuBr2-mediated one-pot two-component oxidative coupling reaction.
Scheme 69: Decarboxylative cyclization route to synthesize 1,3-diarylimidazo[1,5-a]pyridines.
Scheme 70: Mechanistic pathway.
Scheme 71: C–H functionalization reaction of enamines to produce diversified heterocycles.
Scheme 72: A plausible mechanism.
Scheme 73: CuI-promoted aerobic oxidative cyclization reaction of ketoxime acetates and pyridines.
Scheme 74: CuI-catalyzed pathway for the formation of imidazo[1,2-a]pyridine.
Scheme 75: Mechanistic pathway.
Scheme 76: Mechanistic rationale for the synthesis of products.
Scheme 77: Copper-catalyzed synthesis of vinyloxy-IP.
Scheme 78: Regioselective product formation with propiolates.
Scheme 79: Proposed mechanism for vinyloxy-IP formation.
Scheme 80: Regioselective synthesis of 3-hetero-substituted imidazo[1,2-a]pyridines with different reaction su...
Scheme 81: Mechanistic pathway.
Scheme 82: CuI-mediated synthesis of 3-formylimidazo[1,2-a]pyridines.
Scheme 83: Radical pathway for 3-formylated IP synthesis.
Scheme 84: Pd-catalyzed urea-cyclization reaction for IPs.
Scheme 85: Pd-catalyzed one-pot-tandem amination and intramolecular amidation reaction.
Figure 5: Scope of aniline nucleophiles.
Scheme 86: Pd–Cu-catalyzed Sonogashira coupling reaction.
Scheme 87: One-pot amide coupling reaction for the synthesis of imidazo[4,5-b]pyridines.
Scheme 88: Urea cyclization reaction for the synthesis of two series of pyridines.
Scheme 89: Amidation reaction for the synthesis of imidazo[4,5-b]pyridines.
Figure 6: Amide scope.
Scheme 90: Pd NPs-catalyzed 3-component reaction for the synthesis of 2,3-diarylated IPs.
Scheme 91: Plausible mechanistic pathway for Pd NPs-catalyzed MCR.
Scheme 92: Synthesis of chromenoannulated imidazo[1,2-a]pyridines.
Scheme 93: Mechanism for the synthesis of chromeno-annulated IPs.
Scheme 94: Zinc oxide NRs-catalyzed synthesis of imidazo[1,2-a]azines/diazines.
Scheme 95: Zinc oxide-catalyzed isocyanide based GBB reaction.
Scheme 96: Reaction pathway for ZnO-catalyzed GBB reaction.
Scheme 97: Mechanistic pathway.
Scheme 98: ZnO NRs-catalyzed MCR for the synthesis of imidazo[1,2-a]azines.
Scheme 99: Ugi type GBB three-component reaction.
Scheme 100: Magnetic NPs-catalyzed synthesis of imidazo[1,2-a]pyridines.
Scheme 101: Regioselective synthesis of 2-alkoxyimidazo[1,2-a]pyridines catalyzed by Fe-SBA-15.
Scheme 102: Plausible mechanistic pathway for the synthesis of 2-alkoxyimidazopyridine.
Scheme 103: Iron-catalyzed synthetic approach.
Scheme 104: Iron-catalyzed aminooxygenation reaction.
Scheme 105: Mechanistic pathway.
Scheme 106: Rh(III)-catalyzed double C–H activation of 2-substituted imidazoles and alkynes.
Scheme 107: Plausible reaction mechanism.
Scheme 108: Rh(III)-catalyzed non-aromatic C(sp2)–H bond activation–functionalization for the synthesis of imid...
Scheme 109: Reactivity and selectivity of different substrates.
Scheme 110: Rh-catalyzed direct C–H alkynylation by Li et al.
Scheme 111: Suggested radical mechanism.
Scheme 112: Scandium(III)triflate-catalyzed one-pot reaction and its mechanism for the synthesis of benzimidazo...
Scheme 113: RuCl3-assisted Ugi-type Groebke–Blackburn condensation reaction.
Scheme 114: C-3 aroylation via Ru-catalyzed two-component reaction.
Scheme 115: Regioselective synthetic mechanism.
Scheme 116: La(III)-catalyzed one-pot GBB reaction.
Scheme 117: Mechanistic approach for the synthesis of imidazo[1,2-a]pyridines.
Scheme 118: Synthesis of imidazo[1,2-a]pyridine using LaMnO3 NPs under neat conditions.
Scheme 119: Mechanistic approach.
Scheme 120: One-pot 3-CR for regioselective synthesis of 2-alkoxy-3-arylimidazo[1,2-a]pyridines.
Scheme 121: Formation of two possible products under optimization of the catalysts.
Scheme 122: Mechanistic strategy for NiFe2O4-catalyzed reaction.
Scheme 123: Two-component reaction for synthesizing imidazodipyridiniums.
Scheme 124: Mechanistic scheme for the synthesis of imidazodipyridiniums.
Scheme 125: CuI-catalyzed arylation of imidazo[1,2-a]pyridines.
Scheme 126: Mechanism for arylation reaction.
Scheme 127: Cupric acetate-catalyzed double carbonylation approach.
Scheme 128: Radical mechanism for double carbonylation of IP.
Scheme 129: C–S bond formation reaction catalyzed by cupric acetate.
Scheme 130: Cupric acetate-catalyzed C-3 formylation approach.
Scheme 131: Control experiments for signifying the role of DMSO and oxygen.
Scheme 132: Mechanism pathway.
Scheme 133: Copper bromide-catalyzed CDC reaction.
Scheme 134: Extension of the substrate scope.
Scheme 135: Plausible radical pathway.
Scheme 136: Transannulation reaction for the synthesis of imidazo[1,5-a]pyridines.
Scheme 137: Plausible reaction pathway for denitrogenative transannulation.
Scheme 138: Cupric acetate-catalyzed C-3 carbonylation reaction.
Scheme 139: Plausible mechanism for regioselective C-3 carbonylation.
Scheme 140: Alkynylation reaction at C-2 of 3H-imidazo[4,5-b]pyridines.
Scheme 141: Two-way mechanism for C-2 alkynylation of 3H-imidazo[4,5-b]pyridines.
Scheme 142: Palladium-catalyzed SCCR approach.
Scheme 143: Palladium-catalyzed Suzuki coupling reaction.
Scheme 144: Reaction mechanism.
Scheme 145: A phosphine free palladium-catalyzed synthesis of C-3 arylated imidazopyridines.
Scheme 146: Palladium-mediated Buchwald–Hartwig cross-coupling reaction.
Figure 7: Structure of the ligands optimized.
Scheme 147: Palladium acetate-catalyzed direct arylation of imidazo[1,2-a]pyridines.
Scheme 148: Palladium acetate-catalyzed mechanistic pathway.
Scheme 149: Palladium acetate-catalyzed regioselective arylation reported by Liu and Zhan.
Scheme 150: Mechanism for selective C-3 arylation of IP.
Scheme 151: Pd(II)-catalyzed alkenylation reaction with styrenes.
Scheme 152: Pd(II)-catalyzed alkenylation reaction with acrylates.
Scheme 153: A two way mechanism.
Scheme 154: Double C–H activation reaction catalyzed by Pd(OAc)2.
Scheme 155: Probable mechanism.
Scheme 156: Palladium-catalyzed decarboxylative coupling.
Scheme 157: Mechanistic cycle for decarboxylative arylation reaction.
Scheme 158: Ligand-free approach for arylation of imidazo[1,2-a]pyridine-3-carboxylic acids.
Scheme 159: Mechanism for ligandless arylation reaction.
Scheme 160: NHC-Pd(II) complex assisted arylation reaction.
Scheme 161: C-3 arylation of imidazo[1,2-a]pyridines with aryl bromides catalyzed by Pd(OAc)2.
Scheme 162: Pd(II)-catalyzed C-3 arylations with aryl tosylates and mesylates.
Scheme 163: CDC reaction for the synthesis of imidazo[1,2-a]pyridines.
Scheme 164: Plausible reaction mechanism for Pd(OAc)2-catalyzed synthesis of imidazo[1,2-a]pyridines.
Scheme 165: Pd-catalyzed C–H amination reaction.
Scheme 166: Mechanism for C–H amination reaction.
Scheme 167: One-pot synthesis for 3,6-di- or 2,3,6-tri(hetero)arylimidazo[1,2-a]pyridines.
Scheme 168: C–H/C–H cross-coupling reaction of IPs and azoles catalyzed by Pd(II).
Scheme 169: Mechanistic cycle.
Scheme 170: Rh-catalyzed C–H arylation reaction.
Scheme 171: Mechanistic pathway for C–H arylation of imidazo[1,2-a]pyridine.
Scheme 172: Rh(III)-catalyzed double C–H activation of 2-phenylimidazo[1,2-a]pyridines and alkynes.
Scheme 173: Rh(III)-catalyzed mechanistic pathway.
Scheme 174: Rh(III)-mediated oxidative coupling reaction.
Scheme 175: Reactions showing functionalization of the product obtained by the group of Kotla.
Scheme 176: Mechanism for Rh(III)-catalyzed oxidative coupling reaction.
Scheme 177: Rh(III)-catalyzed C–H activation reaction.
Scheme 178: Mechanistic cycle.
Scheme 179: Annulation reactions of 2-arylimidazo[1,2-a]pyridines and alkynes.
Scheme 180: Two-way reaction mechanism for annulations reaction.
Scheme 181: [RuCl2(p-cymene)]2-catalyzed C–C bond formation reaction.
Scheme 182: Reported reaction mechanism.
Scheme 183: Fe(III) catalyzed C-3 formylation approach.
Scheme 184: SET mechanism-catalyzed by Fe(III).
Scheme 185: Ni(dpp)Cl2-catalyzed KTC coupling.
Scheme 186: Pd-catalyzed SM coupling.
Scheme 187: Vanadium-catalyzed coupling of IP and NMO.
Scheme 188: Mechanistic cycle.
Scheme 189: Selective C3/C5–H bond functionalizations by mono and bimetallic systems.
Scheme 190: rGO-Ni@Pd-catalyzed C–H bond arylation of imidazo[1,2-a]pyridine.
Scheme 191: Mechanistic pathway for heterogeneously catalyzed arylation reaction.
Scheme 192: Zinc triflate-catalyzed coupling reaction of substituted propargyl alcohols.
Adhesion, forces and the stability of interfaces
- Robin Guttmann,
- Johannes Hoja,
- Christoph Lechner,
- Reinhard J. Maurer and
- Alexander F. Sax
Beilstein J. Org. Chem. 2019, 15, 106–129, doi:10.3762/bjoc.15.12
Graphical Abstract
Figure 1: Left: The graphs of an interaction potential Vint composed of an attractive component Vatt and a re...
Figure 2: From left to right: An external pulling force acting on the system in its equilibrium structure inc...
Figure 3: Potential functions (thin lines) and the first derivatives (thick lines). Left: For constant ΔV the...
Figure 4: Left: The disk covering the atoms of molecule B seen by an atom in molecule A expands with increasi...
Figure 5: Demonstration of the contact zone and the reduced contact zone of an adsorbate/adsorbent complex wi...
Figure 6: The contact zone of an (8.0)-CNT/tetracene complex. The bold black lines in the traverse section re...
Figure 7: The separation of tetracene from graphene. Top row: Mode S1 (left), mode S2 (right). Bottom row: mo...
Figure 8: The slope functions for the separation of tetracene from graphene for the four separation modes. Re...
Figure 9: Boiling points of straight-chain primary alcohols, straight-chain primary amines and straight-chain...
Spectroelectrochemical studies on the effect of cations in the alkaline glycerol oxidation reaction over carbon nanotube-supported Pd nanoparticles
- Dennis Hiltrop,
- Steffen Cychy,
- Karina Elumeeva,
- Wolfgang Schuhmann and
- Martin Muhler
Beilstein J. Org. Chem. 2018, 14, 1428–1435, doi:10.3762/bjoc.14.120
Graphical Abstract
Figure 1: CVs of the electrooxidation of 1 M glycerol over Pd/NCNT and Pd/OCNT in 1 M KOH at 1000 rpm at a sc...
Figure 2: CVs of the electrooxidation of 1 M glycerol over Pd/NCNT-NH3 and Pd/OCNT-He in 1 M NaOH at 1000 rpm...
Figure 3: Comparison of IR spectra recorded at 0.77 and 1.17 V vs RHE (further potentials are shown in Supporting Information File 1, Figu...
Mechanochemistry of nucleosides, nucleotides and related materials
- Olga Eguaogie,
- Joseph S. Vyle,
- Patrick F. Conlon,
- Manuela A. Gîlea and
- Yipei Liang
Beilstein J. Org. Chem. 2018, 14, 955–970, doi:10.3762/bjoc.14.81
- : specifically, solid solutions, cocrystals, polymorph transitions, carbon nanotube dissolution and inclusion complex formation. Keywords: DNA; green chemistry; mechanochemistry; nucleoside; nucleotide; Introduction Several definitions of mechanochemistry have been attempted since Ostwald included it as one of
Graphical Abstract
Figure 1: Examples of equipment used to perform mechanochemistry on nucleoside and nucleotide substrates (not...
Figure 2: Ganciclovir.
Scheme 1: Nucleoside tritylation effected by hand grinding in a heated mortar and pestle.
Scheme 2: Persilylation of ribonucleoside hydroxy groups (and in situ acylation of cytidine) in a MBM.
Scheme 3: Nucleoside amine and carboxylic acid Boc protection using an improvised attritor-type mill.
Scheme 4: Nucleobase Boc protection via transient silylation using an improvised attritor-type mill.
Scheme 5: Chemoselective N-acylation of an aminonucleoside using LAG in a MBM.
Scheme 6: Azide–alkyne cycloaddition reactions performed in a copper vessel in a MBM.
Figure 3: a) Custom-machined copper vessel and zirconia balls used to perform CuAAC reactions (showing: upper...
Scheme 7: Thiolate displacement reactions of nucleoside derivatives in a MBM.
Scheme 8: Selenocyanate displacement reactions of nucleoside derivatives in a MBM.
Scheme 9: Nucleobase glycosidation reactions and subsequent deacetylation performed in a MBM.
Scheme 10: Regioselective phosphorylation of nicotinamide riboside in a MBM.
Scheme 11: Preparation of nucleoside phosphoramidites in a MBM using ionic liquid-stabilised chlorophosphorami...
Scheme 12: Preparation of a nucleoside phosphite triester using LAG in a MBM.
Scheme 13: Internucleoside phosphate coupling linkages in a MBM.
Scheme 14: Preparation of ADPR analogues using in a MBM.
Scheme 15: Synthesis of pyrophosphorothiolate-linked dinucleoside cap analogues in a MBM to effect hydrolytic ...
Figure 4: Early low temperature mechanised ball mill as described by Mudd et al. – adapted from reference [78].
Scheme 16: Co-crystal grinding of alkylated nucleobases in an amalgam mill (N.B. no frequency was recorded in ...
Figure 5: Materials used to prepare a smectic phase.
Figure 6: Structures of 5-fluorouracil (5FU) and nucleoside analogue prodrugs subject to mechanochemical co-c...
Scheme 17: Preparation of DNA-SWNT complex in a MBM.
Heterogeneous Pd catalysts as emulsifiers in Pickering emulsions for integrated multistep synthesis in flow chemistry
- Katharina Hiebler,
- Georg J. Lichtenegger,
- Manuel C. Maier,
- Eun Sung Park,
- Renie Gonzales-Groom,
- Bernard P. Binks and
- Heidrun Gruber-Woelfler
Beilstein J. Org. Chem. 2018, 14, 648–658, doi:10.3762/bjoc.14.52
- interface populated by catalyst particles. They deposited metallic Pd onto carbon nanotube–inorganic oxide hybrid nanoparticles and used them in emulsions for the hydrodeoxygenation of a phenolic compound and the hydrogenation and etherification of an aldehyde. The advantages of such a system include a high
Graphical Abstract
Figure 1: Targeted integrated multistep synthesis of valsartan (1) and sacubitril (2).
Scheme 1: Suzuki–Miyaura coupling of phenylboronic acid 3 with various bromoarenes 4a–e (a: R1 = H, R2 = CH3; ...
Figure 2: Particle size distribution of Ce0.495Sn0.495Pd0.01O2–δ after size reduction via milling and separat...
Figure 3: Optical microscope images of fresh aqueous dispersions, 0.05 wt %, of (a) Ce0.495Sn0.495Pd0.01O2–δ ...
Figure 4: Photos of vessels containing cyclohexane-in-water emulsions stabilised by particles of Ce0.495Sn0.4...
Figure 5: Optical microscopy images of cyclohexane-in-water emulsions of Figure 4 after one month for particle concen...
Figure 6: (top) Mean emulsion droplet diameter after 30 min as a function of particle concentration for syste...
Figure 7: Mean particle diameter in aqueous dispersions as a function of Ce0.495Sn0.495Pd0.01O2–δ concentrati...
Figure 8: Variation of the zeta potential and pH value of aqueous dispersions of Ce0.495Sn0.495Pd0.01O2–δ par...
Figure 9: (a) Appearance of octane-in-water emulsions with time at 0.05 wt % of Ce0.495Sn0.495Pd0.01O2–δ (lef...
Figure 10: (a) Variation of droplet diameter with particle concentration for octane-in-water emulsions stabili...
Figure 11: (a) Variation of droplet diameter with particle concentration for toluene-in-water emulsions stabil...
Enabling technologies and green processes in cyclodextrin chemistry
- Giancarlo Cravotto,
- Marina Caporaso,
- Laszlo Jicsinszky and
- Katia Martina
Beilstein J. Org. Chem. 2016, 12, 278–294, doi:10.3762/bjoc.12.30
- depicted in Scheme 11, the synthesis generated in situ azomethine ylides which include both a β-CD unit and a DOTAMA tris(t-butyl ester) moiety. The toxicity assessment, cell viability and permeability of single-walled carbon nanotube (SWCNT) platform, was evaluated on five human cell lines. No-toxicity
Graphical Abstract
Figure 1: (a) Multihorn-flow US reactor, (b) Cavitational turbine, (c) Pilot-scale BM, (d) High-pressure MW r...
Figure 2: Trends in CD papers and CD use in green chemical processes.
Figure 3: Distribution of energy efficient methods in CD publications.
Figure 4: Document type dealing with CD chemistry under non-conventional techniques (conference proceedings a...
Figure 5: Document type dealing with sustainable technologies in CD publications.
Scheme 1: Synthesis of 6I-(p-toluenesulfonyl)-β-CD.
Scheme 2: Example of CuAAC with 6I-azido-6I-deoxy-β-CD and phenylacetylene.
Scheme 3: Synthesis of 6I-benzylureido-6I-deoxy-per-O-acetyl-β-CD.
Scheme 4: Synthesis of 3I-azido-3I-deoxy-altro-α, β- and γ-CD.
Scheme 5: Synthesis of 2-2’ bridged bis(β-CDs). Reaction conditions: 1) TBDMSCl, imidazole, dry pyridine, sti...
Scheme 6: Insoluble reticulated CD polymer.
Scheme 7: CD-HDI cross linked polymers.
Scheme 8: Derivatization of 6I-(p-toluenesulfonyl)-β-CD by tosyl displacement.
Scheme 9: Synthetic scheme for the preparation of heptakis(6-amino-6-deoxy)-β-CD, heptakis(6-deoxy-6-ureido)-...
Scheme 10: Structure of CD derivatives obtained via MW-assisted CuAAC.
Scheme 11: Preparation of SWCN CD-DOTA carrier.
Encapsulation of biocides by cyclodextrins: toward synergistic effects against pathogens
- Véronique Nardello-Rataj and
- Loïc Leclercq
Beilstein J. Org. Chem. 2014, 10, 2603–2622, doi:10.3762/bjoc.10.273
- , the following antimicrobial mechanism was proposed: i) the carbon nanotube embedded in water-insoluble cyclodextrin polyurethane polymers pierce the bacterial cell membrane by direct contacts, and ii) the copper nanoparticles release copper inside the bacterial cell. The combination of these two steps
Graphical Abstract
Scheme 1: Principle of resistance mechanisms through selection of the most resistant micro-organism.
Figure 1: Chemical structure of carbendazim.
Scheme 2: Chemical structure of benomyl and its decomposition in aqueous solution.
Figure 2: Chemical structure of enilconazole.
Figure 3: Chemical structure of chloramidophos.
Scheme 3: The complex problem of pentachlorophenol (PCP) degradation.
Figure 4: Chemical structure of DCPE.
Figure 5: Chemical structures of some biocides used in [59].
Figure 6: Chemical structure of miconazole nitrate.
Figure 7: Chemical structures of triclosan and butylparaben.
Figure 8: Chemical structure of ciprofloxacin hydrochloride.
Figure 9: Chemical structure of benzethonium chloride.
Figure 10: Chemical structure of benzalkonium chlorides.
Scheme 4: Multiple equilibria of CD with benzalkonium chloride (BZK) and fluorometholone.
Scheme 5: Competition between co-micellization and biocidal activity observed for didecyldimethylammonium chl...
Scheme 6: Proposed antimicrobial mechanism of encapsulated didecyldimethylammonium chloride by CDs: (1) diffu...
Scheme 7: Inhibition of co-micellization process observed for didecyldimethylammonium chloride, octaethyleneg...
Scheme 8: Schematic representation of biocide release from a chemically cross-linked CD network.
Scheme 9: Proposed Trojan horse mechanism of silver nanoparticles capped by β-CD.
Scheme 10: Proposed mechanism of copper nanoparticles immobilized on carbon nanotube and embedded in water-ins...
Scheme 11: Advantages and drawback of the physicochemical and biopharmaceutical properties of CDs/biocides inc...
Homochiral BINOL-based macrocycles with π-electron-rich, electron-withdrawing or extended spacing units as receptors for C60
- Marco Caricato,
- Silvia Díez González,
- Idoia Arandia Ariño and
- Dario Pasini
Beilstein J. Org. Chem. 2014, 10, 1308–1316, doi:10.3762/bjoc.10.132
- macrocycles [16], and urea-based structures [17] have all been exploited to develop the nanotube concept. Efficient supramolecular receptors for C60 and higher fullerenes have been already reported in the literature and research in this area is still very active [18][19]. Jasti and co-workers have
Graphical Abstract
Scheme 1: Synthesis of macrocycles 3 and 4.
Figure 1: 1H NMR spectra of macrocycles 3a–d, with key proton resonances for the spacing units and key benzyl...
Figure 2: 1H NMR spectroscopy of macrocycles 4a–d, with proton resonances for the spacing units and key benzy...
Figure 3: CD spectra of macrocycles 3b, 3d, 4b, 4d in EtOH (0.5–12 × 10−6 M).
Figure 4: UV–vis titration of C60 (1.8 × 10−4 M) in toluene with increasing amounts of macrocycle 4b (top) an...
Self-assembly of 2,3-dihydroxycholestane steroids into supramolecular organogels as a soft template for the in-situ generation of silicate nanomaterials
- Valeria C. Edelsztein,
- Andrea S. Mac Cormack,
- Matías Ciarlantini and
- Pablo H. Di Chenna
Beilstein J. Org. Chem. 2013, 9, 1826–1836, doi:10.3762/bjoc.9.213
- between the anionic silicate intermediate species and the self-assembled fibrillar network. Keywords: Hansen parameters; nanotube; organogel; self-assembly; supramolecular gel; Introduction Low molecular mass organogelators (LMOGs) have received increasing attention during the last two decades because
Graphical Abstract
Figure 1: Structures of the 2,3-dihydroxycholestane isomers studied in this work.
Figure 2: 3D plots for LMOG 1 and solvent parameters of the tested solvents a) Hansen solubility parameters (δ...
Figure 3: Tg-vs-concentration plots for gels of 1.
Figure 4: SEM images of xerogels from a,b) dichloromethane, and c,d) from dioxane.
Figure 5: Powder X-ray diffraction pattern of the xerogels of 1 from a) n-hexane and b) dichloromethane.
Figure 6: Self-assembly models proposed for LMOG 1, only the left handed helix is shown, head to head hydroge...
Figure 7: SEM images of nanostructured silica obtained from gels of LMOG 1 under the following conditions: 0....
Continuous preparation of carbon-nanotube-supported platinum catalysts in a flow reactor directly heated by electric current
- Alicja Schlange,
- Antonio Rodolfo dos Santos,
- Ulrich Kunz and
- Thomas Turek
Beilstein J. Org. Chem. 2011, 7, 1412–1420, doi:10.3762/bjoc.7.165
- demonstrate, for the first time, a simple and cost-effective method for the preparation of carbon-nanotube-supported Pt catalysts by using a continuously operated tubular flow reactor. The heating concept was realized by passing electrical current directly through the reactor wall. The experimental setup is
- preparation method is one of the most important factors determining the morphology and activity of Pt catalysts supported by carbon nanotubes. Short heating times and short reaction times are essential for the reduction of highly active platinum particles on nanotube supports. The proposed continuous
- , washed several times with deionised water to a desired pH value of 7 and finally dried in an oven at 60 °C for 24 h. Preparation of electrocatalysts Carbon nanotube supported Pt catalysts were synthesized by the polyol synthesis method (ethylene glycol mediated reaction). The procedure was as follows
Graphical Abstract
Figure 1: Experimental setup for catalyst synthesis in the tubular flow reactor; 1: Reaction mixture reservoi...
Figure 2: Measured temperature profile along the tubular reactor.
Figure 3: TGA weight loss curves for pristine CNT, HNO3 oxidized CNT, Pt/CNT-oil bath and Pt/CNT-tubular reac...
Figure 4: TEM micrographs of catalyst samples: a) Pt/CNT tubular reactor and b) Pt/CNT oil bath.
Figure 5: X-ray diffraction patterns for the as-received CNT and the three Pt/CNT samples taken at intervals ...
Figure 6: Comparison of performance in DMFC with Pt/CNT oil bath and Pt/CNT tubular reactor samples as cathod...
