Search for "biodiesel" in Full Text gives 13 result(s) in Beilstein Journal of Organic Chemistry.
Beilstein J. Org. Chem. 2025, 21, 2389–2415, doi:10.3762/bjoc.21.184
Graphical Abstract
Figure 1: Versatile compounds via cycloaddition reactions.
Scheme 1: Molecular structures of parent compounds 1a–f, 2a–d and cycloadducts 3a–u.
Figure 2: a) Radar view of the physical properties of methyl laurate. b) Oral toxicity values of methyl laura...
Figure 3: The oral toxicity values of all the solvents utilized in the present study obtained with ProTox 3.0....
Figure 4: Ecological, environmental risk assessments, pesticide similarity and biodegradability assessments o...
Figure 5: Ecological, environmental risk assessments, pesticide similarity and biodegradability assessments o...
Figure 6: Ecological, environmental risk assessments, pesticide similarity and biodegradability assessments o...
Figure 7: Various toxicity parameters of methyl laurate and a series of other solvents calculated by ADMETLab...
Figure 8: a) Visualization of the localization of conventional organic and bio-based solvents in the Hansen s...
Figure 9: Vapour pressures of the solvents used (values retrieved from the Chemeo molecular database).
Scheme 2: Endo and exo stereoisomeric approaches of nitrone 1a and maleimide 2a in [3 + 2] cycloaddition reac...
Figure 10: Signals of protons used in the calculation of the diastereomeric ratios (cis/trans) of cycloadditio...
Figure 11: Results of studies on the recovery of solvents used in the reaction.
Figure 12: Simplified scheme describing the reaction monitoring and solvent recovery.
Figure 13: a) The superimposed spectra of C,N-diphenylnitrone and N-phenylmaleimide. b) The spectrum of methyl...
Beilstein J. Org. Chem. 2025, 21, 1520–1527, doi:10.3762/bjoc.21.114
Graphical Abstract
Figure 1: XRD pattern of CS600.
Scheme 1: The transesterification of soybean oil with various alcohols in the presence of CS600 catalyst. Rea...
Scheme 2: The transesterification of various esters with methanol in the presence of CS600 as catalyst. React...
Scheme 3: Gram-scale batch process for the transesterification of soybean oil with methanol. Reaction conditi...
Figure 2: CS600 reusability test. Reaction conditions: 2 wt % CS600, MeOH/4a ratio is 12:1, 65 °C, 4 h.
Figure 3: XRD patterns of the CS600 catalyst after the 1st reaction cycle: A) after washing with methanol and...
Beilstein J. Org. Chem. 2022, 18, 688–706, doi:10.3762/bjoc.18.70
Graphical Abstract
Figure 1: Inductive heating, a powerful tool in industry and the Life Sciences.
Figure 2: Electric displacement field of a ferromagnetic and superparamagnetic material.
Figure 3: Temperature profiles of reactors heated conventionally and by RF heating (Figure 3 redrawn from [24]).
Scheme 1: Continuous flow synthesis of isopulegol (2) from citronellal (1).
Scheme 2: Dry (reaction 1) and steam (reaction 2) methane reforming.
Scheme 3: Calcination and RF heating.
Scheme 4: The continuously operated “Sabatier” process.
Scheme 5: Biofuel production from biomass using inductive heating for pyrolysis.
Scheme 6: Water electrolysis using an inductively heated electrolysis cell.
Scheme 7: Dimroth rearrangement (reaction 1) and three-component reaction (reaction 2) to propargyl amines 8 ...
Figure 4: A. Flow reactor filled with magnetic nanostructured particles (MagSilicaTM) and packed bed reactor ...
Scheme 8: Claisen rearrangement in flow: A. comparison between conventional heating (external oil bath), micr...
Scheme 9: Continuous flow reactions and comparison with batch reaction (oil bath). A. Pd-catalyzed transfer h...
Scheme 10: Continuous flow reactions and comparison with batch reaction (oil bath). A. pericyclic reactions an...
Scheme 11: Reactions under flow conditions using inductively heated fixed-bed materials serving as stoichiomet...
Scheme 12: Reactions under flow conditions using inductively heated fixed-bed materials serving as catalysts: ...
Scheme 13: Two step flow protocol for the preparation of 1,1'-diarylalkanes 77 from ketones and aldehydes 74, ...
Scheme 14: O-Alkylation, the last step in the multistep flow synthesis of Iloperidone (80) accompanied with a ...
Scheme 15: Continuous two-step flow process consisting of Grignard reaction followed by water elimination bein...
Scheme 16: Inductively heated continuous flow protocol for the synthesis of Iso E Super (88) [91,92].
Scheme 17: Three-step continuous flow synthesis of macrocycles 89 and 90 with musk-like olfactoric properties.
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.
Beilstein J. Org. Chem. 2021, 17, 1001–1040, doi:10.3762/bjoc.17.82
Graphical Abstract
Figure 1: Tautomeric forms of biguanide.
Figure 2: Illustrations of neutral, monoprotonated, and diprotonated structures biguanide.
Figure 3: The main approaches for the synthesis of biguanides. The core structure is obtained via the additio...
Scheme 1: The three main preparations of biguanides from cyanoguanidine.
Scheme 2: Synthesis of butylbiguanide using CuCl2 [16].
Scheme 3: Synthesis of biguanides by the direct fusion of cyanoguanidine and amine hydrochlorides [17,18].
Scheme 4: Synthesis of ethylbiguanide and phenylbiguanide as reported by Smolka and Friedreich [14].
Scheme 5: Synthesis of arylbiguanides through the reaction of cyanoguanidine with anilines in water [19].
Scheme 6: Synthesis of aryl- and alkylbiguanides by adaptations of Cohn’s procedure [20,21].
Scheme 7: Microwave-assisted synthesis of N1-aryl and -dialkylbiguanides [22,23].
Scheme 8: Synthesis of aryl- and alkylbiguanides by trimethylsilyl activation [24,26].
Scheme 9: Synthesis of phenformin analogs by TMSOTf activation [27].
Scheme 10: Synthesis of N1-(1,2,4-triazolyl)biguanides [28].
Scheme 11: Synthesis of 2-guanidinobenzazoles by addition of ortho-substituted anilines to cyanoguanidine [30,32] and...
Scheme 12: Synthesis of 2,4-diaminoquinazolines by the addition of 2-cyanoaniline to cyanoguanidine and from 3...
Scheme 13: Reactions of anthranilic acid and 2-mercaptobenzoic acid with cyanoguanidine [24,36,37].
Scheme 14: Synthesis of disubstituted biguanides with Cu(II) salts [38].
Scheme 15: Synthesis of an N1,N2,N5-trisubstituted biguanide by fusion of an amine hydrochloride and 2-cyano-1...
Scheme 16: Synthesis of N1,N5-disubstituted biguanides by the addition of anilines to cyanoguanidine derivativ...
Scheme 17: Microwave-assisted additions of piperazine and aniline hydrochloride to substituted cyanoguanidines ...
Scheme 18: Synthesis of N1,N5-alkyl-substituted biguanides by TMSOTf activation [27].
Scheme 19: Additions of oxoamines hydrochlorides to dimethylcyanoguanidine [49].
Scheme 20: Unexpected cyclization of pyridylcyanoguanidines under acidic conditions [50].
Scheme 21: Example of industrial synthesis of chlorhexidine [51].
Scheme 22: Synthesis of symmetrical N1,N5-diarylbiguanides from sodium dicyanamide [52,53].
Scheme 23: Synthesis of symmetrical N1,N5-dialkylbiguanides from sodium dicyanamide [54-56].
Scheme 24: Stepwise synthesis of unsymmetrical N1,N5-trisubstituted biguanides from sodium dicyanamide [57].
Scheme 25: Examples for the synthesis of unsymmetrical biguanides [58].
Scheme 26: Examples for the synthesis of an 1,3-diaminobenzoquinazoline derivative by the SEAr cyclization of ...
Scheme 27: Major isomers formed by the SEAr cyclization of symmetric biguanides derived from 2- and 3-aminophe...
Scheme 28: Lewis acid-catalyzed synthesis of 8H-pyrrolo[3,2-g]quinazoline-2,4-diamine [63].
Scheme 29: Synthesis of [1,2,4]oxadiazoles by the addition of hydroxylamine to dicyanamide [49,64].
Scheme 30: Principle of “bisamidine transfer” and analogy between the reactions with N-amidinopyrazole and N-a...
Scheme 31: Representative syntheses of N-amidino-amidinopyrazole hydrochloride [68,69].
Scheme 32: First examples of biguanide syntheses using N-amidino-amidinopyrazole [66].
Scheme 33: Example of “biguanidylation” of a hydrazide substrate [70].
Scheme 34: Example for the synthesis of biguanides using S-methylguanylisothiouronium iodide as “bisamidine tr...
Scheme 35: Synthesis of N-substituted N1-cyano-S-methylisothiourea precursors.
Scheme 36: Addition routes on N1-cyano-S-methylisothioureas.
Scheme 37: Synthesis of an hydroxybiguanidine from N1-cyano-S-methylisothiourea [77].
Scheme 38: Synthesis of an N1,N2,N3,N4,N5-pentaarylbiguanide from the corresponding triarylguanidine and carbo...
Scheme 39: Reactions of N,N,N’,N’-tetramethylguanidine (TMG) with carbodiimides to synthesize hexasubstituted ...
Scheme 40: Microwave-assisted addition of N,N,N’,N’-tetramethylguanidine to carbodiimides [80].
Scheme 41: Synthesis of N1-aryl heptasubstituted biguanides via a one-pot biguanide formation–copper-catalyzed ...
Scheme 42: Formation of 1,2-dihydro-1,3,5-triazine derivatives by the reaction of guanidine with excess carbod...
Scheme 43: Plausible mechanism for the spontaneous cyclization of triguanides [82].
Scheme 44: a) Formation of mono- and disubstituted (iso)melamine derivatives by the reaction of biguanides and...
Scheme 45: Reactions of 2-aminopyrimidine with carbodiimides to synthesize 2-guanidinopyrimidines as “biguanid...
Scheme 46: Non-catalyzed alternatives for the addition of 2-aminopyrimidine derivatives to carbodiimides. A) h...
Scheme 47: Addition of guanidinomagnesium halides to substituted cyanamides [90].
Scheme 48: Microwave-assisted synthesis of [11C]metformin by the reaction of 11C-labelled dimethylcyanamide an...
Scheme 49: Formation of 4-amino-6-dimethylamino[1,3,5]triazin-2-ol through the reaction of Boc-guanidine and d...
Scheme 50: Formation of 1,3,5-triazine derivatives via the addition of guanidines to substituted cyanamides [92].
Scheme 51: Synthesis of biguanide by the reaction of O-alkylisourea and guanidine [93].
Scheme 52: Aromatic nucleophilic substitution of guanidine on 2-O-ethyl-1,3,5-triazine [95].
Scheme 53: Synthesis of N1,N2-disubstituted biguanides by the reaction of guanidine and thioureas in the prese...
Scheme 54: Cyclization reactions involving condensations of guanidine(-like) structures with thioureas [97,98].
Scheme 55: Condensations of guanidine-like structures with thioureas [99,100].
Scheme 56: Condensations of guanidines with S-methylisothioureas [101,102].
Scheme 57: Addition of 2-amino-1,3-diazaaromatics to S-alkylisothioureas [103,104].
Scheme 58: Addition of guanidines to 2-(methylsulfonyl)pyrimidines [105].
Scheme 59: An example of a cyclodesulfurization reaction to a fused 3,5-diamino-1,2,4-triazole [106].
Scheme 60: Ring-opening reactions of 1,3-diaryl-2,4-bis(arylimino)-1,3-diazetidines [107].
Scheme 61: Formation of 3,5-diamino-1,2,4-triazole derivatives via addition of hydrazines to 1,3-diazetidine-2...
Scheme 62: Formation of a biguanide via the addition of aniline to 1,2,4-thiadiazol-3,5-diamines, ring opening...
Figure 4: Substitution pattern of biguanides accessible by synthetic pathways a–h.
Beilstein J. Org. Chem. 2018, 14, 2745–2770, doi:10.3762/bjoc.14.253
Graphical Abstract
Figure 1: Different types of sulfonated materials as acid catalysts.
Scheme 1: Synthetic route of 3-methyl-1-sulfo-1H-imidazolium metal chloride ILs and their catalytic applicati...
Scheme 2: Synthetic route of 1,3-disulfo-1H-imidazolium transition metal chloride ILs and their catalytic app...
Scheme 3: Synthetic route of 1,3-disulfoimidazolium carboxylate ILs and their catalytic applications in the s...
Scheme 4: Synthetic route of [BiPy](HSO3)2Cl2 and [Dsim]HSO4 ILs and their catalytic applications for the syn...
Scheme 5: The catalytic applications of (C4(DABCO-SO3H)2·4Cl) IL for the synthesis of spiro-isatin derivative...
Scheme 6: The catalytic applications of (C4(DABCO-SO3H)2·4Cl) IL for the synthesis of bis 2-amino-4H-pyran de...
Scheme 7: The synthetic route of N,N-disulfo-1,1,3,3-tetramethylguanidinium carboxylate ILs and their catalyt...
Scheme 8: The catalytic application of 1-methyl-3-sulfo-1H-imidazolium tetrachloroferrate IL in the synthesis...
Scheme 9: The synthetic route of 3-sulfo-1H-imidazolopyrimidinium hydrogen sulfate IL and its catalytic appli...
Scheme 10: The results for the synthesis of bis(indolyl)methanes and di(bis(indolyl)methyl)benzenes in the pre...
Scheme 11: The catalytic applications of 1-(1-sulfoalkyl)-3-methylimidazolium chloride acidic ILs for the hydr...
Scheme 12: The synthetic route of immobilized 1,4-diazabicyclo[2.2.2]octanesulfonic acid chloride on SiO2 and ...
Scheme 13: The catalytic application of a silica-bonded sulfoimidazolium chloride for the synthesis of 12-aryl...
Scheme 14: The synthetic route of the SBA-15-Ph-SO3H and its catalytic applications for the synthesis of 2H-in...
Scheme 15: The synthetic route for heteropolyanion-based ionic liquids immobilized on mesoporous silica SBA-15...
Scheme 16: Some mechanism aspects of SSA catalyst for the protection of amine derivatives.
Scheme 17: The synthetic route for MWCNT-SO3H and its catalytic application for the synthesis of N-substituted...
Scheme 18: The sulfonic acid-functionalized polymers (P-SO3H) covalently grafted on multi-walled carbon nanotu...
Scheme 19: The transesterification reaction in the presence of S-MWCNTs.
Scheme 20: The synthetic route for the new hypercrosslinked supermicroporous polymer via the Friedel–Crafts al...
Scheme 21: The synthetic route for a new microporous copolymer via the Friedel–Crafts alkylation reaction of t...
Scheme 22: The synthetic route for sulfonated polynaphthalene and its catalytic application for the amidoalkyl...
Scheme 23: The synthetic route of the acidic carbon material and its catalytic application in the etherificatio...
Scheme 24: The synthetic route of the acidic carbon materials and their catalytic applications for the esterif...
Scheme 25: The sulfonated MWCNTs.
Scheme 26: The sulfonated nanoscaled diamond powder for the dehydration of D-xylose into furfural.
Scheme 27: The synthetic route and catalytic application of the GR-SO3H.
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...
Beilstein J. Org. Chem. 2017, 13, 19–25, doi:10.3762/bjoc.13.3
Graphical Abstract
Scheme 1: PEG-assisted grinding strategy for the preparation of 3,5-disubstituted hydantoins.
Beilstein J. Org. Chem. 2016, 12, 2719–2730, doi:10.3762/bjoc.12.268
Graphical Abstract
Figure 1: Electron-transfer initiated activation of α-diketones (background) and present study.
Scheme 1: Proposed dianionic pathway for the cross-benzoin-like reaction of benzils 1 with aldehydes 2 under ...
Scheme 2: Trapping experiment.
Figure 2: Conversion of the 1a/2a coupling in microreactor R5 operated for 150 h at 50 °C.
Beilstein J. Org. Chem. 2016, 12, 1911–1924, doi:10.3762/bjoc.12.181
Graphical Abstract
Scheme 1: The transesterification of diethyl oxalate (DEO) with phenol catalyzed by MoO3/SiO2.
Scheme 2: Transesterification of a triglyceride (TG) with DMC for biodiesel production using KOH as the base ...
Scheme 3: Top: Green methylation of phosphines and amines by dimethyl carbonate (Q = N, P). Bottom: anion met...
Figure 1: Structures of some representative SILs and PILs systems. MCF is a silica-based mesostructured mater...
Scheme 4: Synthesis of the acid polymeric IL. EGDMA: ethylene glycol dimethacrylate.
Scheme 5: The transesterification of sec-butyl acetate with MeOH catalyzed by some acidic imidazolium ILs.
Figure 2: Representative examples of ionic liquids for biodiesel production.
Scheme 6: Top: phosgenation of methanol; middle: EniChem and Ube processes; bottom: Asahi process for the pro...
Scheme 7: The transesterification in the synthesis of organic carbonates.
Scheme 8: The transesterification of DMC with alcohols and diols.
Scheme 9: Transesterification of glycerol with DMC in the presence of 1-n-butyl-3-methylimidazolium-2-carboxy...
Scheme 10: Synthesis of the BMIM-2-CO2 catalyst from butylimidazole and DMC.
Scheme 11: Plausible cooperative (nucleophilic–electrophilic) mechanism for the transesterification of glycero...
Scheme 12: Synthesis of diazabicyclo[5.4.0]undec-7-ene-based ionic liquids.
Scheme 13: Synthesis of the DABCO–DMC ionic liquid.
Scheme 14: Cooperative mechanism of ionic liquid-catalyzed glycidol production.
Scheme 15: [TMA][OH]-catalyzed synthesis of glycidol (GD) from glycerol and dimethyl carbonate [46].
Scheme 16: [BMIM]OH-catalyzed synthesis of DPC from DMC and 1-pentanol.
Figure 3: Representative examples of ionic liquids for biodiesel production.
Figure 4: Acyclic non-symmetrical organic carbonates synthetized with 1-(trimethoxysilyl)propyl-3-methylimida...
Scheme 17: A simplified reaction mechanism for DMC production.
Scheme 18: [P8881][MeOCO2] metathesis with acetic acid and phenol.
Figure 5: Examples of carbonates obtained through transesterification using phosphonium salts as catalysts.
Scheme 19: Examples of carbonates obtained from different bio-based diols using [P8881][CH3OCO2] as catalyst.
Scheme 20: Ambiphilic catalysis for transesterification reactions in the presence of carbonate phosphonium sal...
Beilstein J. Org. Chem. 2015, 11, 2370–2387, doi:10.3762/bjoc.11.259
Graphical Abstract
Figure 1: Biocatalytic routes for conversion of CO2 into compounds with carbon in the reduced oxidation state...
Figure 2: Carbonic anhydrase-catalysed rapid interconversion of CO2 and HCO3− in living systems.
Scheme 1: The Calvin cycle for fixation of CO2 with RuBisCO.
Scheme 2: The reductive TCA cycle with CO2 fixation enzymes designated.
Scheme 3: The Wood–Ljungdahl pathway for generation of acetyl-CoA through reduction of CO2 to formate and CO....
Scheme 4: The acyl-CoA carboxylase pathways for autotrophic CO2 fixation. ACC: acetyl-CoA/propionyl-CoA carbo...
Figure 3: RuBisCO CO2-fixing bypass installed in E. coli and S. cerevisiae to increase carbon flux toward pro...
Scheme 5: Integrated biocatalytic system for carboxylation of phosphoenolpyruvate (19), using PEPC and carbon...
Scheme 6: PEPC and pyruvate carboxylase catalysed carboxylation of pyruvate backbone for the generation of ox...
Scheme 7: Decarboxylase catalysed carboxylation of (a) phenol derivatives, (b) indole and (c) pyrrole.
Figure 4: Formate dehydrogenase (FDH) catalysed reversible reduction of CO2 to formate with electron donor re...
Figure 5: Sequential generation of formate, formaldehyde and methanol from CO2 using reducing equivalents sou...
Figure 6: Hydrogen storage as formic acid through biocatalytic hydrogenation of CO2 and subsequent on-demand ...
Figure 7: Schematic showing required flow of reducing equivalents for CO2 fixation through biotechnological a...
Beilstein J. Org. Chem. 2015, 11, 1194–1219, doi:10.3762/bjoc.11.134
Graphical Abstract
Figure 1: Pharmaceutical structures targeted in early flow syntheses.
Scheme 1: Flow synthesis of 6-hydroxybuspirone (9). Inserted photograph reprinted with permission from [45]. Copy...
Figure 2: Configuration of a baffled reactor tube (left) and its schematic working principle (right).
Scheme 2: McQuade’s flow synthesis of ibuprofen (16).
Scheme 3: Jamison’s flow synthesis of ibuprofen sodium salt (17).
Scheme 4: Flow synthesis of imatinib (23).
Scheme 5: Flow synthesis of the potent 5HT1B antagonist 28.
Scheme 6: Flow synthesis of a selective δ-opioid receptor agonist 33.
Scheme 7: Flow synthesis of a casein kinase I inhibitor library (38).
Scheme 8: Flow synthesis of fluoxetine (46).
Scheme 9: Flow synthesis of artemisinin (55).
Scheme 10: Telescoped flow synthesis of artemisinin (55) and derivatives (62–64).
Scheme 11: Flow approach towards AZD6906 (65).
Scheme 12: Pilot scale flow synthesis of key intermediate 73.
Scheme 13: Semi-flow synthesis of vildagliptine (77).
Scheme 14: Pilot scale asymmetric flow hydrogenation towards 83. Inserted photograph reprinted with permission...
Figure 3: Schematic representation of the ‘tube-in-tube’ reactor.
Scheme 15: Flow synthesis of fanetizole (87) via tube-in-tube system.
Scheme 16: Flow synthesis of diphenhydramine.HCl (92).
Scheme 17: Flow synthesis of rufinamide (95).
Scheme 18: Large scale flow synthesis of rufinamide precursor 102.
Scheme 19: First stage in the flow synthesis of meclinertant (103).
Scheme 20: Completion of the flow synthesis of meclinertant (103).
Scheme 21: Flow synthesis of olanzapine (121) utilising inductive heating techniques.
Scheme 22: Flow synthesis of amitriptyline·HCl (127).
Scheme 23: Flow synthesis of E/Z-tamoxifen (132) using peristaltic pumping modules.
Figure 4: Container sized portable mini factory (photograph credit: INVITE GmbH, Leverkusen Germany).
Scheme 24: Flow synthesis of imidazo[1,2-a]pyridines 136 linked to frontal affinity chromatography (FAC).
Figure 5: Structures of zolpidem (142) and alpidem (143).
Scheme 25: Synthesis and screening loops in the discovery of new Abl kinase inhibitors.
Figure 6: Schotten–Baumann approach towards LY573636.Na (147).
Scheme 26: Pilot scale flow synthesis of LY2886721 (146).
Scheme 27: Continuous flow manufacture of alikiren hemifumarate 152.
Beilstein J. Org. Chem. 2013, 9, 1957–1968, doi:10.3762/bjoc.9.232
Graphical Abstract
Scheme 1: Mesoscale production of heterocycles in a continuous flow microwave reactor [44-46].
Scheme 2: The original Bohlmann–Rahtz synthesis of pyridines [49].
Scheme 3: Bohlmann–Rahtz synthesis of pyridine 2b.
Figure 1: Microwave flow reactor for the Bohlmann–Rahtz synthesis of pyridine 2b.
Scheme 4: Four-component synthesis of Hantzsch DHP 15a,b.
Scheme 5: Three- or four-component synthesis of Hantzsch DHP 15c,d.