Search for "H2O2" in Full Text gives 147 result(s) in Beilstein Journal of Organic Chemistry.
Beilstein J. Org. Chem. 2017, 13, 1982–1993, doi:10.3762/bjoc.13.194
Graphical Abstract
Figure 1: Overview of the preparation of the nanocomposites based on iron oxide and polysaccharide.
Figure 2: XPS spectra of A: Fe2O3-PS4, B: Fe2O3-PS4-MNP and C: TiO2-Fe2O3-PS4 nanohybrids.
Figure 3: A and B: SEM and TEM images of TiO2-Fe2O3-PS4; C and D: SEM and TEM images of Fe2O3-PS4. E and F: S...
Figure 4: DRIFT spectra of A: TiO2-Fe2O3-PS4 and B: Fe2O3-PS4-MNP nanohybrids.
Scheme 1: Oxidation of benzyl alcohol to benzaldehyde.
Figure 5: Conversion and selectivity of the oxidation of benzyl alcohol for the three catalytic systems.
Scheme 2: Microwave-assisted alkylation of toluene with benzyl chloride.
Figure 6: Conversion and selectivity of the microwave-assisted alkylation of toluene for the three catalytic ...
Scheme 3: Alkylation of toluene with benzyl chloride with conventional heating.
Figure 7: Conversion and selectivity of the alkylation of toluene with conventional heating for the three cat...
Figure 8: Reusability of the iron oxide/polysaccharide nanohybrids.
Beilstein J. Org. Chem. 2017, 13, 1753–1769, doi:10.3762/bjoc.13.170
Graphical Abstract
Scheme 1: Generally accepted ion-pairing mechanism between the chiral cation Q+ of a PTC and an enolate and s...
Scheme 2: Reported asymmetric α-fluorination of β-ketoesters 1 using different chiral PTCs.
Scheme 3: Asymmetric α-fluorination of benzofuranones 4 with phosphonium salt PTC F1.
Scheme 4: Asymmetric α-fluorination of 1 with chiral phosphate-based catalysts.
Scheme 5: Anionic PTC-catalysed α-fluorination of enamines 7 and ketones 10.
Scheme 6: PTC-catalysed α-chlorination reactions of β-ketoesters 1.
Scheme 7: Shioiri’s seminal report of the asymmetric α-hydroxylation of 15 with chiral ammonium salt PTCs.
Scheme 8: Asymmetric ammonium salt-catalysed α-hydroxylation using oxygen together with a P(III)-based reduct...
Scheme 9: Asymmetric ammonium salt-catalysed α-photooxygenations.
Scheme 10: Asymmetric ammonium salt-catalysed α-hydroxylations using organic oxygen-transfer reagents.
Scheme 11: Asymmetric triazolium salt-catalysed α-hydroxylation with in situ generated peroxy imidic acid 24.
Scheme 12: Phase-transfer-catalysed dearomatization of phenols and naphthols.
Scheme 13: Ishihara’s ammonium salt-catalysed oxidative cycloetherification.
Scheme 14: Chiral phase-transfer-catalysed α-sulfanylation reactions.
Scheme 15: Chiral phase-transfer-catalysed α-trifluoromethylthiolation of β-ketoesters 1.
Scheme 16: Chiral phase-transfer-catalysed α-amination of β-ketoesters 1 using diazocarboxylates 38.
Scheme 17: Asymmetric α-fluorination of benzofuranones 4 using diazocarboxylates 38 in the presence of phospho...
Scheme 18: Anionic phase-transfer-catalysed α-amination of β-ketoesters 1 with aryldiazonium salts 41.
Scheme 19: Triazolium salt L-catalysed α-amination of different prochiral nucleophiles with in situ activated ...
Scheme 20: Phase-transfer-catalysed Neber rearrangement.
Beilstein J. Org. Chem. 2017, 13, 1596–1660, doi:10.3762/bjoc.13.159
Graphical Abstract
Figure 1: Initial proposal for the core macrolactone structure (left) and the established complete structure ...
Figure 2: Mycolactone congeners and their origins.
Figure 3: Misassigned mycolactone E structure according to Small et al. [50] (11) and the correct structure (6) f...
Figure 4: Schematic illustration of Kishi’s improved mycolactone TLC detection method exploiting derivatizati...
Figure 5: Fluorescent probes derived from natural mycolactone A/B (1a,b) or its synthetic 8-desmethyl analogs...
Figure 6: Tool compounds used by Pluschke and co-workers for elucidating the molecular targets of mycolactone...
Figure 7: Synthetic strategies towards the extended mycolactone core. A) General strategies. B) Kishi’s appro...
Scheme 1: Kishi’s 1st generation approach towards the extended core structure of mycolactones. Reagents and c...
Scheme 2: Kishi’s 2nd generation approach towards the extended core structure of mycolactones. Reagents and c...
Scheme 3: Kishi’s 3rd generation approach towards the extended core structure of mycolactones. Reagents and c...
Scheme 4: Negishi’s synthesis of the extended core structure of mycolactones. Reagents and conditions: a) (i) ...
Scheme 5: Burkart’s (incomplete) 1st generation approach towards the extended core structure of mycolactones....
Scheme 6: Burkart’s (incomplete) 1st, 2nd and 3rd generation approach towards the extended mycolactone core s...
Scheme 7: Altmann’s synthesis of alkyl iodide 91. Reagents and conditions: a) (i) PMB-trichloroacetimidate, T...
Scheme 8: Final steps of Altmann’s synthesis of the extended core structure of mycolactones. Reagents and con...
Scheme 9: Basic principles of the Aggarwal lithiation–borylation homologation process [185,186].
Scheme 10: Aggarwal’s synthesis of the C1–C11 fragment of the mycolactone core. Reagents and conditions: a) Cl...
Scheme 11: Aggarwal’s synthesis of the linear C1–C20 fragment of the mycolactone core. Reagents and conditions...
Figure 8: Synthetic strategies towards the mycolactone A/B lower side chain.
Scheme 12: Gurjar and Cherian’s synthesis of the C1’–C8’ fragment of the mycolactone A/B pentaenoate side chai...
Scheme 13: Gurjar and Cherian’s synthesis of the benzyl-protected mycolactone A/B pentaenoate side chain. Reag...
Scheme 14: Kishi’s synthesis of model compounds for elucidating the stereochemistry of the C7’–C16’ fragment o...
Scheme 15: Kishi’s synthesis of the mycolactone A/B pentaenoate side chain. (a) (i) NaH, (EtO)2P(O)CH2CO2Et, T...
Scheme 16: Feringa and Minnaard's incomplete synthesis of mycolactone A/B pentaenoate side chain. Reagents and...
Scheme 17: Altmann’s approach towards the mycolactone A/B pentaenoate side chain. Reagents and conditions: a) ...
Scheme 18: Negishi’s access to the C1’–C7’ fragment of mycolactone A. Reagents and conditions: a) (i) n-BuLi, ...
Scheme 19: Negishi’s approach to the C1’–C7’ fragment of mycolactone B. Reagents and conditions: a) (i) DIBAL-...
Scheme 20: Negishi’s synthesis of the C8’–C16’ fragment of mycolactone A/B. Reagents and conditions: a) 142, BF...
Scheme 21: Negishi’s assembly of the mycolactone A and B pentaenoate side chains. Reagents and conditions: a) ...
Scheme 22: Blanchard’s approach to the mycolactone A/B pentaenoate side chain. a) (i) Ph3P=C(Me)COOEt, CH2Cl2,...
Scheme 23: Kishi’s approach to the mycolactone C pentaenoate side chain exemplified for the 13’R,15’S-isomer 1...
Scheme 24: Altmann’s (unpublished) synthesis of the mycolactone C pentaenoate side chain. Reagents and conditi...
Scheme 25: Blanchard’s synthesis of the mycolactone C pentaenoate side chain. Reagents and conditions: a) (i) ...
Scheme 26: Kishi’s synthesis of the tetraenoate side chain of mycolactone F exemplified by enantiomer 165. Rea...
Scheme 27: Kishi’s synthesis of the mycolactone E tetraenoate side chain. Reagents and conditions: a) (i) CH2=...
Scheme 28: Wang and Dai’s synthesis of the mycolactone E tetraenoate side chain. Reagents and conditions: a) (...
Scheme 29: Kishi’s synthesis of the dithiane-protected tetraenoate side chain of the minor oxo-metabolite of m...
Scheme 30: Kishi’s synthesis of the mycolactone S1 and S2 pentaenoate side chains. Reagents and conditions: a)...
Scheme 31: Kishi’s 1st generation and Altmann’s total synthesis of mycolactone A/B (1a,b) and Negishi’s select...
Scheme 32: Kishi’s 2nd generation total synthesis of mycolactone A/B (1a,b). Reagents and conditions: a) 2,4,6...
Scheme 33: Blanchard’s synthesis of the 8-desmethylmycolactone core. Reagents and conditions: a) (i) TsCl, TEA...
Scheme 34: Altmann’s (partially unpublished) synthesis of the C20-hydroxylated mycolactone core. Reagents and ...
Scheme 35: Altmann’s and Blanchard’s approaches towards the 11-isopropyl-8-desmethylmycolactone core. Reagents...
Scheme 36: Blanchard’s synthesis of the saturated variant of the C11-isopropyl-8-desmethylmycolactone core. Re...
Scheme 37: Structure elucidation of photo-mycolactones generated from tetraenoate 224.
Scheme 38: Kishi’s synthesis of the linear precursor of the photo-mycolactone B1 lower side chain. Reagents an...
Scheme 39: Kishi’s synthesis of the photo-mycolactone B1 lower side chain. Reagents and conditions: a) LiTMP, ...
Scheme 40: Kishi’s synthesis of a stabilized lower mycolactone side chain. Reagents and conditions: a) (i) TBD...
Scheme 41: Blanchard’s variation of the C12’,C13’,C15’ stereocluster. Reagents and conditions: a) (i) DIBAL-H,...
Scheme 42: Blanchard’s synthesis of aromatic mycolactone polyenoate side chain analogs. Reagents and condition...
Scheme 43: Small’s partial synthesis of a BODIPY-labeled mycolactone derivative and Demangel’s partial synthes...
Scheme 44: Blanchard’s synthesis of the BODIPY-labeled 8-desmethylmycolactones. Reagents and conditions: a) (i...
Scheme 45: Altmann’s synthesis of biotinylated mycolactones. Reagents and conditions: a) (i) CDI, THF, rt, 2 d...
Figure 9: Kishi’s elongated n-butyl carbamoyl mycolactone A/B analog.
Beilstein J. Org. Chem. 2017, 13, 1439–1445, doi:10.3762/bjoc.13.141
Graphical Abstract
Figure 1: N2 isotherms of (a) RGO, (b) Fe/RGO, and (c) Co/RGO.
Figure 2: SEM images of (a and b) RGO, (c) 1% Fe/RGO, and (d) 1% Co/RGO.
Figure 3: TEM micrographs at different magnifications of (a and b) RGO, (c and d) 1% Fe/RGO, and (e and f) 1%...
Figure 4: Powder XRD patterns of RGO supported Fe and Co NPs.
Figure 5: IR spectra of 1% Fe/RGO and 1% Co/RGO catalysts collected by using diffuse reflectance infrared tra...
Beilstein J. Org. Chem. 2017, 13, 1280–1287, doi:10.3762/bjoc.13.124
Graphical Abstract
Figure 1: Elansolids A1/A2, B1, B2 and A3 (1–4).
Scheme 1: IMDA to generate the tetrahydroindane unit of the elansolids by oxidation of benzyl ether 8 as prec...
Scheme 2: Stille cross-coupling reaction and formation of eastern fragment 13.
Scheme 3: Total synthesis of elansolids B1 (2) and B2 (3).
Beilstein J. Org. Chem. 2017, 13, 910–918, doi:10.3762/bjoc.13.92
Graphical Abstract
Scheme 1: One-pot synthesis of vinyl and alkynyl selenides.
Scheme 2: Effect of t-BuOK on the formation of n-octyl alkynyl selenide 5a.
Scheme 3: Effect of reactants concentration on alkynyl selenide formation.
Scheme 4: Synthesis of N-ethyl-2-(n-octylselanyl)-1H-indole (9) and 3-iodo-2-(n-octylselanyl)benzofuran (10).
Scheme 5: Control reactions and mechanistic study.
Scheme 6: Proposed mechanism for the formation of selenides 5.
Scheme 7: Proposed mechanism for the formation of indole 9.
Beilstein J. Org. Chem. 2017, 13, 659–664, doi:10.3762/bjoc.13.65
Graphical Abstract
Scheme 1: Synthetic route to 3,5-disubstituted isoxazoles.
Beilstein J. Org. Chem. 2017, 13, 589–611, doi:10.3762/bjoc.13.58
Graphical Abstract
Figure 1: Examples of drugs bearing phenol or aryl thiol as central structural motifs.
Scheme 1: Hydroxylation of aryl halides using biphenylphosphine as ligand.
Scheme 2: Hydroxylation of aryl halides using tert-butylphosphine as ligand.
Scheme 3: Hydroxylation of aryl halides using imidazole typed phosphine ligands.
Scheme 4: [Pd(cod)(CH2SiMe3)2] catalyzed hydroxylation of aryl halides.
Scheme 5: Pd/PANI catalyzed hydroxylation of hydroxylation of aryl halides.
Scheme 6: MCM-41-dzt-Pd catalyzed hydroxylation of aryl halides.
Scheme 7: Hydroxylation of aryl halides using dibenzoylmethane as ligand.
Scheme 8: Hydroxylation of aryl halides using 2,2’-bipyridine as ligand.
Scheme 9: Hydroxylation of aryl bromides using imidazolyl pyridine as ligand.
Scheme 10: Hydroxylation of aryl halides using DMEDA as ligand.
Scheme 11: Hydroxylation of aryl halides using PAO as ligand.
Scheme 12: Hydroxylation of aryl halides using D-glucose as ligand.
Scheme 13: Hydroxylation of aryl halides using INDION-770 as ligand.
Scheme 14: PEG-400 mediated hydroxylation of aryl halides.
Scheme 15: Hydroxylation of aryl halides using glycolic acid as ligand.
Scheme 16: Hydroxylation of aryl halides using L-sodium ascorbate as ligand.
Scheme 17: Difunctionalized ethanes mediated hydroxylation of aryl iodides.
Scheme 18: Hydroxylation of aryl halides using 2-methyl-8-hydroxylquinoline as ligand.
Scheme 19: Hydroxylation of aryl halides using 8-hydroxyquinolin-N-oxide as ligand.
Scheme 20: Hydroxylation of aryl halides using lithium pipecolinate as ligand.
Scheme 21: Hydroxylation of aryl halides using L-lithium prolinate.
Scheme 22: Hydroxylation of aryl halides using triethanolamine as ligand.
Scheme 23: CuI-nanoparticle-catalyzed hydroxylation of aryl halides.
Scheme 24: Cu-g-C3N4-catalyzed hydroxylation of aryl bromides.
Scheme 25: Cu(OAc)2-mediated hydroxylation of (2-pyridyl)arenes.
Scheme 26: Removable pyridine moiety directed hydroxylation of arenes.
Scheme 27: Removable quinoline moiety directed hydroxylation of arenes.
Scheme 28: CuCl2 catalyzed hydroxylation of benzimidazoles and benzoxazoles.
Scheme 29: Disulfide-directed C–H hydroxylation.
Scheme 30: Pd(OAc)2-catalyzed hydroxylation of diarylpyridines.
Scheme 31: PdCl2-catalyzed hydroxylation of 2-arylpyridines.
Scheme 32: PdCl2-catalyzed hydroxylation of 2-arylpyridines.
Scheme 33: Pd(OAc)2-catalyzed hydroxylation of 2-arylpyridines.
Scheme 34: Pd(CH3CN)2Cl2-catalyzed hydroxylation of 2-arylpyridines.
Scheme 35: Pd(OAc)2-catalyzed hydroxylation of benzothiazolylarenes.
Scheme 36: Pd(OAc)2 catalyzed hydroxylation of benzimidazolylarenes.
Scheme 37: Dioxane mediated hydroxylation of 2-heteroarylarenes.
Scheme 38: Hydroxylation of oxime methyl ester.
Scheme 39: CN-directed meta-hydroxylation.
Scheme 40: Pd(OAc)2-catalyzed hydroxylation of benzoic acids.
Scheme 41: Pd(OAc)2-catalyzed hydroxylation of biaryl or aryl alkyl ketones.
Scheme 42: Pd(OAc)2 and Pd(TFA)2 catalyzed hydroxylation of aryl ketones.
Scheme 43: Pd(OAc)2 catalyzed hydroxylation of aryl ketones.
Scheme 44: Pd(TFA)2-catalyzed hydroxylation of aryl phosphonates.
Scheme 45: Hydroxy group directed hydroxylation.
Scheme 46: [Ru(O2CMes)2(p-cymene)] catalyzed hydroxylation of benzamides and aryl ketones.
Scheme 47: [RuCl2(p-cymene)]2-catalyzed hydroxylation of benzamides and carbamates.
Scheme 48: [RuCl2(p-cymene)]2 catalyzed hydroxylation of benzaldehydes.
Scheme 49: [RuCl2(p-cymene)]2 catalyzed hydroxylation of ethyl benzoates, benzamides and carbamates.
Scheme 50: Different regioselective ortho-hydroxylation.
Scheme 51: Ruthenium-complex-catalyzed hydroxylation of flavones.
Scheme 52: Vanadium-catalyzed hydroxylation of arenes.
Scheme 53: VOSiW-catalyzed hydroxylation of arenes.
Scheme 54: Synthesis of aryl thiols using thiourea as thiol source.
Scheme 55: Synthesis of aryl thiols using alkyl thiol as thiol source.
Scheme 56: Synthesis of 1-thionaphthol using HS-TIPS as thiol source.
Scheme 57: Synthesis of aryl thiols using sodium thiosulfate as thiol source.
Scheme 58: Synthesis of thiophenol using thiobenzoic acid as thiol source.
Scheme 59: Synthesis of aryl thiols using sulfur powder as thiol source.
Scheme 60: CuI-nanoparticles catalyzed synthesis of aryl thiols.
Scheme 61: Synthesis of aryl thiols using Na2S·5H2O as thiol source.
Scheme 62: Synthesis of aryl thiols using 1,2-ethanedithiol as thiol source.
Beilstein J. Org. Chem. 2017, 13, 571–578, doi:10.3762/bjoc.13.56
Graphical Abstract
Figure 1: The chroman-based antihypertensive drug nebivolol, its biologically active stereoisomers and late-s...
Scheme 1: Synthetic strategies toward late-stage intermediates of 1a.
Scheme 2: Attempted synthesis of (±)-2 via intramolecular SNAr reaction.
Scheme 3: Speculation on the synthesis of a 2-substituted chroman derivative based on Borhan’s approach.
Scheme 4: Synthesis of syn-2,3-dihydroxy esters 19 and 20.
Scheme 5: Attempted cyclization according to Borhan’s method.
Scheme 6: Synthesis of β-hydroxy-α-tosyloxy esters 24 and 25.
Scheme 7: Speculation of simultaneous epoxidation/epoxide-ring opening.
Scheme 8: Synthesis of chroman diols 2 and 29, respectively.
Scheme 9: Conversion of 32 into 3 via Mitsunobu inversion.
Scheme 10: Synthesis of chroman epoxide 5.
Beilstein J. Org. Chem. 2017, 13, 393–404, doi:10.3762/bjoc.13.42
Graphical Abstract
Figure 1: Adsorption of RNA on natural carbonate mineral samples.
Figure 2: Co-precipitation experiments on carbonate minerals for RNA-binding competition. The precipitated co...
Figure 3: RNA-induced calcium carbonate polymorphism. A: Feigl’s stain of CaCO3 precipitate formed by double ...
Figure 4: RNA adsorbed on aragonite is resistant to thermal degradation in aqueous solution. 18% denaturing P...
Beilstein J. Org. Chem. 2017, 13, 164–173, doi:10.3762/bjoc.13.19
Graphical Abstract
Figure 1: Structure of the S. pneumoniae serotype 12F capsular polysaccharide repeating unit [15].
Scheme 1: Retrosynthetic analyses of the S. pneumoniae hexasaccharide 1.
Scheme 2: Attempted synthesis of mannosazide building block 15. Reagents and conditions: (a) levulinic acid, ...
Scheme 3: Synthesis of mannosazide building block 18. Reagents and conditions: (a) TBSCl, imidazole, DCM, 0 °...
Scheme 4: Synthesis of the reducing-end trisaccharide 3. Reagents and conditions: (a) TMSOTf, (CH3CH2)2O/CH2Cl...
Scheme 5: Synthesis of monosaccharide building blocks 8, 9 and 26. Reagents and conditions: (a) acetic anhydr...
Scheme 6: Synthesis of the non-reducing end trisaccharide 2. Reagents and conditions: (a) TMSOTf, CH2Cl2, −30...
Scheme 7: Attempted synthesis of hexasaccharide repeating unit 36 via a convergent [3 + 3] glycosylation stra...
Scheme 8: Linear assembly of fully protected hexasaccharide 51. Reagents and conditions: (a) DDQ, CH2Cl2/MeOH...
Scheme 9: Global deprotection to furnish S. pneumonia serotype 12F repeating unit hexasaccharide 1. Reagents ...
Beilstein J. Org. Chem. 2016, 12, 2873–2882, doi:10.3762/bjoc.12.286
Graphical Abstract
Figure 1: Adsorption of β-CD on the surface of nanoTiO2 [37].
Figure 2: Turbidity of nanoTiO2 dispersion (0.02%) in the presence of 1% HPBCD-P (green diamond) and 1% CMBCD...
Figure 3: Aggregation effect of 0.1% NaCl on 0.02% nanoTiO2 dispersion in the absence (green curve) and prese...
Figure 4: Aggregation effect of tap water on 0.02% nanoTiO2 dispersion in the absence (green curve) and prese...
Figure 5: Photodegradation of MB in aqueous solutions: distilled water (A), 0.1% NaCl solution (B) and tap wa...
Figure 6: Photodegradation of IBR in distilled water examining the drug itself (blue circle), and in the pres...
Beilstein J. Org. Chem. 2016, 12, 2443–2449, doi:10.3762/bjoc.12.237
Graphical Abstract
Figure 1: Chemical structures of parylene N, parylene C, and parylene D.
Figure 2: Chemical structures of [2.2]paracyclophane and 4,7,12,15-tetrachloro[2.2]paracyclophane.
Scheme 1: Synthesis of substituted (4-methylbenzyl)trimethylammonium bromides from substituted (4-methylbenzy...
Beilstein J. Org. Chem. 2016, 12, 2173–2180, doi:10.3762/bjoc.12.207
Graphical Abstract
Scheme 1: Synthesis of levulinic acid from ligno-cellulosic feedstocks and its principal uses to access fine ...
Figure 1: Anchoring methodologies: a) impregnation; b) covalent binding.
Figure 2: Activity of the supported sulfonic acid catalyst within the first six cycles. Reaction conditions: ...
Beilstein J. Org. Chem. 2016, 12, 1949–1980, doi:10.3762/bjoc.12.184
Graphical Abstract
Scheme 1: Nitroso hetero-Diels–Alder reaction.
Scheme 2: The hetero-Diels–Alder reaction between thebaine (4) and an acylnitroso dienophile 5.
Figure 1: Examples of nitroso dienophiles frequently used in hetero-Diels–Alder reaction studies.
Scheme 3: Synthesis of arylnitroso species by substitution of a trifluoroborate group [36].
Scheme 4: Synthesis of arylnitroso compounds by amine oxidation.
Scheme 5: Synthesis of arylnitroso compounds by hydroxylamine oxidation.
Scheme 6: Synthesis of chloronitroso compounds by the treatment of a nitronate anion with oxalyl chloride.
Scheme 7: Non-oxidative routes to acylnitroso species.
Figure 2: RB3LYP/6-31G* computed energies (in kcal·mol−1) and bond lengths for exo and endo-transition states...
Scheme 8: Hetero-Diels–Alder cycloadditions of diene 28 and nitroso dienophiles 29.
Figure 3: Relative reactivity (ΔE#) and regioselectivity (Δ) for hetero-Diels–Alder of 28 and nitroso dienoph...
Scheme 9: Reaction of chiral 1-phosphono-1,3-butadiene 31 with nitroso dienophiles 32.
Scheme 10: Hetero-Diels–Alder reactions of hydroxamic acids 35 with various dienes 37.
Scheme 11: General regioselectivity of the nitroso hetero-Diels–Alder reaction observed with unsymmetrical die...
Scheme 12: Effect of the nitroso species on the regioselectivity for weakly directing 2-substituted dienes.
Scheme 13: Regioselectivity of 1,4-disubstituted dienes 51.
Scheme 14: Nitroso hetero-Diels–Alder reaction between Boc-nitroso compound 54 and dienes 55.
Scheme 15: Nitroso hetero-Diels–Alder reaction between Wightman reagent 58 and dienes 59.
Scheme 16: Regioselective reaction of 3-dienyl-2-azetidinones 62 with nitrosobenzene (47).
Scheme 17: The regioselective reaction of 1,3-butadienes 65 with various nitroso heterodienophiles 66.
Scheme 18: Catalysis of the nitroso hetero-Diels–Alder reaction by vanadium in the presence of the oxidant CHP...
Figure 4: 1,2-Oxazines synthesized in solution with moderate to high regioselectivity, showing the favored re...
Figure 5: 1,2-Oxazines synthesized in the solid phase with moderate to high regioselectivity, showing the fav...
Scheme 19: Regioselectivity of solution-phase nitroso hetero-Diels–Alder reaction with acyl and aryl nitroso d...
Scheme 20: Favored regioisomeric outcome for the solution and solid-phase reactions, giving hetero-Diels–Alder...
Figure 6: Favored regioisomers and regioisomeric ratios for 1,2-oxazines synthesized in solid phase (91, 93, ...
Scheme 21: Regiocontrol of the reaction between 3-dienyl-2-azetidinones and nitrosobenzene due to change in a ...
Scheme 22: Regiocontrol of the reaction between diene 111 and 2-methyl-6-nitrosopyridine (112) due to metal co...
Scheme 23: Asymmetric hetero-Diels–Alder reactions reported by Vasella [56].
Scheme 24: Asymmetric hetero-Diels–Alder reaction of cyclohexa-1,3-diene (120) with acylnitroso dienophile 119....
Scheme 25: Asymmetric induction with L-proline derivatives 124–126.
Scheme 26: Asymmetric cycloaddition of the acylnitroso compound 136 to diene 135.
Scheme 27: Asymmetric induction with arylmenthol-based nitroso dienophiles 142.
Scheme 28: Cycloaddition of silyloxycyclohexadiene 145 to the acylnitroso dienophile derived from (+)-camphors...
Scheme 29: Asymmetric reaction of O-isopropylidene-protected cis-cyclohexa-3,5-diene-1,2-diol 147 with mannofu...
Scheme 30: Synthesis of synthon 152 from 2-methoxyphenol 150 and chiral auxiliary 151.
Scheme 31: Asymmetric nitroso hetero-Diels–Alder reaction with Wightman chloronitroso reagent 58.
Scheme 32: Asymmetric 1,2-oxazine synthesis using chiral cyclic diene 157 and the application of this reaction...
Scheme 33: Asymmetric 1,2-oxazine synthesis using a chiral diene reported by Jones et al. [75]. aRegioisomeric rat...
Scheme 34: The nitroso hetero-Diels–Alder reaction of acyclic oxazolidine-substituted diene 170 and chiral 1-s...
Scheme 35: The nitroso hetero-Diels–Alder reaction of acyclic lactam-substituted diene 176 with various acylni...
Scheme 36: The hetero-Diels–Alder reaction of acylnitroso dienophile.
Scheme 37: The hetero-Diels–Alder reaction of arylnitroso dienophiles using Lewis acids.
Scheme 38: Asymmetric hetero-Diels–Alder reactions of chiral alkyl N-dienylpyroglutamates.
Scheme 39: Catalytic asymmetric arylnitroso reaction between mono-substituted 1,3-cyclohexadiene 196 and disub...
Figure 7: Plausible chelate intermediate complexes formed during the hetero-Diels–Alder reaction to give 1,2-...
Scheme 40: Catalytic asymmetric nitroso hetero-Diels–Alder between cyclic dienes and 2-nitrosopyridine.
Scheme 41: The reason for the increased enantioselectivity of stereoisomer 212 compared with stereoisomer 213.
Scheme 42: The copper-catalyzed nitroso hetero-Diels–Alder reaction of 6-methyl-2-nitrosopyridine (199) with p...
Scheme 43: Asymmetric nitroso hetero-Diels–Alder reaction of nitrosoarenes with dienylcarbamates catalyzed by ...
Scheme 44: The enantioselective hetero-Diels–Alder reaction between nitrosobenzene and (E)-2,4-pentadien-1-ol (...
Scheme 45: Asymmetric nitroso hetero-Diels–Alder reaction using tartaric acid ester chelation of the diene and...
Beilstein J. Org. Chem. 2016, 12, 1647–1748, doi:10.3762/bjoc.12.162
Graphical Abstract
Figure 1: The named transformations considered in this review.
Scheme 1: The Baeyer–Villiger oxidation.
Scheme 2: The general mechanism of the peracid-promoted Baeyer–Villiger oxidation.
Scheme 3: General mechanism of the Lewis acid-catalyzed Baeyer–Villiger rearrangement.
Scheme 4: The theoretically studied mechanism of the BV oxidation reaction promoted by H2O2 and the Lewis aci...
Scheme 5: Proton movements in the transition states of the Baeyer–Villiger oxidation.
Scheme 6: The dependence of the course of the Baeyer–Villiger oxidation on the type of O–O-bond cleavage in t...
Scheme 7: The acid-catalyzed Baeyer–Villiger oxidation of cyclic epoxy ketones 22.
Scheme 8: Oxidation of isophorone oxide 29.
Scheme 9: Synthesis of acyl phosphate 32 from acyl phosphonate 31.
Scheme 10: Synthesis of aflatoxin B2 (36).
Scheme 11: The Baeyer–Villiger rearrangement of ketones 37 to lactones 38.
Scheme 12: Synthesis of 3,4-dimethoxybenzoic acid (40) via Baeyer–Villiger oxidation.
Scheme 13: Oxone transforms α,β-unsaturated ketones 43 into vinyl acetates 44.
Scheme 14: The Baeyer–Villiger oxidation of ketones 45 using diaryl diselenide and hydrogen peroxide.
Scheme 15: Baeyer–Villiger oxidation of (E)-2-methylenecyclobutanones.
Scheme 16: Oxidation of β-ionone (56) by H2O2/(BnSe)2 with formation of (E)-2-(2,6,6-trimethylcyclohex-1-en-1-...
Scheme 17: The mechanism of oxidation of ketones 58a–f by hydrogen peroxide in the presence of arsonated polys...
Scheme 18: Oxidation of ketone (58b) by H2O2 to 6-methylcaprolactone (59b) catalyzed by Pt complex 66·BF4.
Scheme 19: Oxidation of ketones 67 with H2O2 in the presence of [(dppb}Pt(µ-OH)]22+.
Scheme 20: The mechanism of oxidation of ketones 67 in the presence of [(dppb}Pt(µ-OH)]22+ and H2O2.
Scheme 21: Oxidation of benzaldehydes 69 in the presence of the H2O2/MeReO3 system.
Scheme 22: Oxidation of acetophenones 72 in the presence of the H2O2/MeReO3 system.
Scheme 23: Baeyer–Villiger oxidation of 2-adamantanone (45c) in the presence of Sn-containing mesoporous silic...
Scheme 24: Aerobic Baeyer–Villiger oxidation of ketones 76 using metal-free carbon.
Scheme 25: A regioselective Baeyer-Villiger oxidation of functionalized cyclohexenones 78 into a dihydrooxepin...
Scheme 26: The oxidation of aldehydes and ketones 80 by H2O2 catalyzed by Co4HP2Mo15V3O62.
Scheme 27: The cleavage of ketones 82 with hydrogen peroxide in alkaline solution.
Scheme 28: Oxidation of ketones 85 to esters 86 with H2O2–urea in the presence of KHCO3.
Scheme 29: Mechanism of the asymmetric oxidation of cyclopentane-1,2-dione 87a with the Ti(OiPr)4/(+)DET/t-BuO...
Scheme 30: The oxidation of cis-4-tert-butyl-2-fluorocyclohexanone (93) with m-chloroperbenzoic acid.
Scheme 31: The mechanism of the asymmetric oxidation of 3-substituted cyclobutanone 96a in the presence of chi...
Scheme 32: Enantioselective Baeyer–Villiger oxidation of cyclic ketones 98.
Scheme 33: Regio- and enantioselective Baeyer–Villiger oxidation of cyclic ketones 101.
Scheme 34: The proposed mechanism of the Baeyer–Villiger oxidation of acetal 105f.
Scheme 35: Synthesis of hydroxy-10H-acridin-9-one 117 from tetramethoxyanthracene 114.
Scheme 36: The Baeyer–Villiger oxidation of the fully substituted pyrrole 120.
Scheme 37: The Criegee rearrangement.
Scheme 38: The mechanism of the Criegee reaction of a peracid with a tertiary alcohol 122.
Scheme 39: Criegee rearrangement of decaline ethylperoxoate 127 into ketal 128.
Scheme 40: The ionic cleavage of 2-methoxy-2-propyl perester 129.
Scheme 41: The Criegee rearrangement of α-methoxy hydroperoxide 136.
Scheme 42: Synthesis of enol esters and acetals via the Criegee rearrangement.
Scheme 43: Proposed mechanism of the transformation of 1-hydroperoxy-2-oxabicycloalkanones 147a–d.
Scheme 44: Transformation of 3-hydroxy-1,2-dioxolanes 151 into diketone derivatives 152.
Scheme 45: Criegee rearrangement of peroxide 153 with the mono-, di-, and tri-O-insertion.
Scheme 46: The sequential Criegee rearrangements of adamantanes 157a,b.
Scheme 47: Synthesis of diaryl carbonates 160a–d from triarylmethanols 159a–d through successive oxygen insert...
Scheme 48: The synthesis of sesquiterpenes 162 from ketone 161 with a Criegee rearrangement as one key step.
Scheme 49: Synthesis of trans-hydrindan derivatives 164, 165.
Scheme 50: The Hock rearrangement.
Scheme 51: The general scheme of the cumene process.
Scheme 52: The Hock rearrangement of aliphatic hydroperoxides.
Scheme 53: The mechanism of solvolysis of brosylates 174a–c and spiro cyclopropyl carbinols 175a–c in THF/H2O2....
Scheme 54: The fragmentation mechanism of hydroperoxy acetals 178 to esters 179.
Scheme 55: The acid-catalyzed rearrangement of phenylcyclopentyl hydroperoxide 181.
Scheme 56: The peroxidation of tertiary alcohols in the presence of a catalytic amount of acid.
Scheme 57: The acid-catalyzed reaction of bicyclic secondary alcohols 192 with hydrogen peroxide.
Scheme 58: The photooxidation of 5,6-disubstituted 3,4-dihydro-2H-pyrans 196.
Scheme 59: The oxidation of tertiary alcohols 200a–g, 203a,b, and 206.
Scheme 60: Transformation of functional peroxide 209 leading to 2,3-disubstitued furans 210 in one step.
Scheme 61: The synthesis of carbazoles 213 via peroxide rearrangement.
Scheme 62: The construction of C–N bonds using the Hock rearrangement.
Scheme 63: The synthesis of moiety 218 from 217 which is a structural motif in the antitumor–antibiotic of CC-...
Scheme 64: The in vivo oxidation steps of cholesterol (219) by singlet oxygen.
Scheme 65: The proposed mechanism of the rearrangement of cholesterol-5α-OOH 220.
Scheme 66: Photochemical route to artemisinin via Hock rearrangement of 223.
Scheme 67: The Kornblum–DeLaMare rearrangement.
Scheme 68: Kornblum–DeLaMare transformation of 1-phenylethyl tert-butyl peroxide (225).
Scheme 69: The synthesis 4-hydroxyenones 230 from peroxide 229.
Scheme 70: The Kornblum–DeLaMare rearrangement of peroxide 232.
Scheme 71: The reduction of peroxide 234.
Scheme 72: The Kornblum–DeLaMare rearrangement of endoperoxide 236.
Scheme 73: The rearrangement of peroxide 238 under Kornblum–DeLaMare conditions.
Scheme 74: The proposed mechanism of rearrangement of peroxide 238.
Scheme 75: The Kornblum–DeLaMare rearrangement of peroxides 242a,b.
Scheme 76: The base-catalyzed rearrangements of bicyclic endoperoxides having electron-withdrawing substituent...
Scheme 77: The base-catalyzed rearrangements of bicyclic endoperoxides 249a,b having electron-donating substit...
Scheme 78: The base-catalyzed rearrangements of bridge-head substituted bicyclic endoperoxides 251a,b.
Scheme 79: The Kornblum–DeLaMare rearrangement of hydroperoxide 253.
Scheme 80: Synthesis of β-hydroxy hydroperoxide 254 from endoperoxide 253.
Scheme 81: The amine-catalyzed rearrangement of bicyclic endoperoxide 263.
Scheme 82: The base-catalyzed rearrangement of meso-endoperoxide 268 into 269.
Scheme 83: The photooxidation of 271 and subsequent Kornblum–DeLaMare reaction.
Scheme 84: The Kornblum–DeLaMare rearrangement as one step in the oxidation reaction of enamines.
Scheme 85: The Kornblum–DeLaMare rearrangement of 3,5-dihydro-1,2-dioxenes 284, 1,2-dioxanes 286, and tert-but...
Scheme 86: The Kornblum–DeLaMare rearrangement of epoxy dioxanes 290a–d.
Scheme 87: Rearrangement of prostaglandin H2 292.
Scheme 88: The synthesis of epicoccin G (297).
Scheme 89: The Kornblum–DeLaMare rearrangement used in the synthesis of phomactin A.
Scheme 90: The Kornblum–DeLaMare rearrangement in the synthesis of 3H-quinazolin-4-one 303.
Scheme 91: The Kornblum–DeLaMare rearrangement in the synthesis of dolabriferol (308).
Scheme 92: Sequential transformation of 3-substituted 2-pyridones 309 into 3-hydroxypyridine-2,6-diones 311 in...
Scheme 93: The Kornblum–DeLaMare rearrangement of peroxide 312 into hydroxy enone 313.
Scheme 94: The Kornblum–DeLaMare rearrangement in the synthesis of polyfunctionalized carbonyl compounds 317.
Scheme 95: The Kornblum–DeLaMare rearrangement in the synthesis of (Z)-β-perfluoroalkylenaminones 320.
Scheme 96: The Kornblum–DeLaMare rearrangement in the synthesis of γ-ketoester 322.
Scheme 97: The Kornblum–DeLaMare rearrangement in the synthesis of diterpenoids 326 and 328.
Scheme 98: The synthesis of natural products hainanolidol (331) and harringtonolide (332) from peroxide 329.
Scheme 99: The synthesis of trans-fused butyrolactones 339 and 340.
Scheme 100: The synthesis of leucosceptroid C (343) and leucosceptroid P (344) via the Kornblum–DeLaMare rearra...
Scheme 101: The Dakin oxidation of arylaldehydes or acetophenones.
Scheme 102: The mechanism of the Dakin oxidation.
Scheme 103: A solvent-free Dakin reaction of aromatic aldehydes 356.
Scheme 104: The organocatalytic Dakin oxidation of electron-rich arylaldehydes 358.
Scheme 105: The Dakin oxidation of electron-rich arylaldehydes 361.
Scheme 106: The Dakin oxidation of arylaldehydes 358 in water extract of banana (WEB).
Scheme 107: A one-pot approach towards indolo[2,1-b]quinazolines 364 from indole-3-carbaldehydes 363 through th...
Scheme 108: The synthesis of phenols 367a–c from benzaldehydes 366a-c via acid-catalyzed Dakin oxidation.
Scheme 109: Possible transformation paths of the highly polarized boric acid coordinated H2O2–aldehyde adduct 3...
Scheme 110: The Elbs oxidation of phenols 375 to hydroquinones.
Scheme 111: The mechanism of the Elbs persulfate oxidation of phenols 375 affording p-hydroquinones 376.
Scheme 112: Oxidation of 2-pyridones 380 under Elbs persulfate oxidation conditions.
Scheme 113: Synthesis of 3-hydroxy-4-pyridone (384) via an Elbs oxidation of 4-pyridone (382).
Scheme 114: The Schenck rearrangement.
Scheme 115: The Smith rearrangement.
Scheme 116: Three main pathways of the Schenck rearrangement.
Scheme 117: The isomerization of hydroperoxides 388 and 389.
Scheme 118: Trapping of dioxacyclopentyl radical 392 by oxygen.
Scheme 119: The hypothetical mechanism of the Schenck rearrangement of peroxide 394.
Scheme 120: The autoxidation of oleic acid (397) with the use of labeled isotope 18O2.
Scheme 121: The rearrangement of 18O-labeled hydroperoxide 400 under an atmosphere of 16O2.
Scheme 122: The rearrangement of the oleate-derived allylic hydroperoxides (S)-421 and (R)-425.
Scheme 123: Mechanisms of Schenck and Smith rearrangements.
Scheme 124: The rearrangement and cyclization of 433.
Scheme 125: The Wieland rearrangement.
Scheme 126: The rearrangement of bis(triphenylsilyl) 439 or bis(triphenylgermyl) 441 peroxides.
Scheme 127: The oxidative transformation of cyclic ketones.
Scheme 128: The hydroxylation of cyclohexene (447) in the presence of tungstic acid.
Scheme 129: The oxidation of cyclohexene (447) under the action of hydrogen peroxide.
Scheme 130: The reaction of butenylacetylacetone 455 with hydrogen peroxide.
Scheme 131: The oxidation of bridged 1,2,4,5-tetraoxanes.
Scheme 132: The proposed mechanism for the oxidation of bridged 1,2,4,5-tetraoxanes.
Scheme 133: The rearrangement of ozonides.
Scheme 134: The acid-catalyzed oxidative rearrangement of malondialdehydes 462 under the action of H2O2.
Scheme 135: Pathways of the Lewis acid-catalyzed cleavage of dialkyl peroxides 465 and ozonides 466.
Scheme 136: The mechanism of the transformation of (tert-butyldioxy)cyclohexanedienones 472.
Scheme 137: The synthesis of Vitamin K3 from 472a.
Scheme 138: Proposed mechanism for the transformation of 478d into silylated endoperoxide 479d.
Scheme 139: The rearrangement of hydroperoxide 485 to form diketone 486.
Scheme 140: The base-catalyzed rearrangement of cyclic peroxides 488a–g.
Scheme 141: Synthesis of chiral epoxides and aldols from peroxy hemiketals 491.
Scheme 142: The multistep transformation of (R)-carvone (494) to endoperoxides 496a–e.
Scheme 143: The decomposition of anthracene endoperoxide 499.
Scheme 144: Synthesis of esters 503 from aldehydes 501 via rearrangement of peroxides 502.
Scheme 145: Two possible paths for the base-promoted decomposition of α-azidoperoxides 502.
Scheme 146: The Story decomposition of cyclic diperoxide 506a.
Scheme 147: The Story decomposition of cyclic triperoxide 506b.
Scheme 148: The thermal rearrangement of endoperoxides A into diepoxides B.
Scheme 149: The transformation of peroxide 510 in the synthesis of stemolide (511).
Scheme 150: The possible mechanism of the rearrangement of endoperoxide 261g.
Scheme 151: The photooxidation of indene 517.
Scheme 152: The isomerization of ascaridole (523).
Scheme 153: The isomerization of peroxide 525.
Scheme 154: The thermal transformation of endoperoxide 355.
Scheme 155: The photooxidation of cyclopentadiene (529) at a temperature higher than 0 °C.
Scheme 156: The thermal rearrangement of endoperoxides 538a,b.
Scheme 157: The transformation of peroxides 541.
Scheme 158: The thermal rearrangements of strained cyclic peroxides.
Scheme 159: The thermal rearrangement of diacyl peroxide 551 in the synthesis of C4-epi-lomaiviticin B core 553....
Scheme 160: The 1O2 oxidation of tryptophan (554) and rearrangement of dioxetane intermediate 555.
Scheme 161: The Fe(II)-promoted cleavage of aryl-substituted bicyclic peroxides.
Scheme 162: The proposed mechanism of the Fe(II)-promoted rearrangement of 557a–c.
Scheme 163: The reaction of dioxolane 563 with Fe(II) sulfate.
Scheme 164: Fe(II)-promoted rearrangement of 1,2-dioxane 565.
Scheme 165: Fe(II) cysteinate-promoted rearrangement of 1,2-dioxolane 568.
Scheme 166: The transformation of 1,2-dioxanes 572a–c under the action of FeCl2.
Scheme 167: Fe(II) cysteinate-promoted transformation of tetraoxane 574.
Scheme 168: The CoTPP-catalyzed transformation of bicyclic endoperoxides 600a–d.
Scheme 169: The CoTPP-catalyzed transformation of epoxy-1,2-dioxanes.
Scheme 170: The Ru(II)-catalyzed reactions of 1,4-endoperoxide 261g.
Scheme 171: The Ru(II)-catalyzed transformation as a key step in the synthesis of elyiapyrone A (610) from 1,4-...
Scheme 172: Peroxides with antimalarial activity.
Scheme 173: The interaction of iron ions with artemisinin (616).
Scheme 174: The interaction of FeCl2 with 1,2-dioxanes 623, 624.
Scheme 175: The mechanism of reaction 623 and 624 with Fe(II)Cl2.
Scheme 176: The reaction of bicyclic natural endoperoxides G3-factors 631–633 with FeSO4.
Scheme 177: The transformation of terpene cardamom peroxide 639.
Scheme 178: The different ways of the cleavage of tetraoxane 643.
Scheme 179: The LC–MS analysis of interaction of tetraoxane 646 with iron(II)heme 647.
Scheme 180: The rearrangement of 3,6-epidioxy-1,10-bisaboladiene (EDBD, 649).
Scheme 181: Easily oxidized substrates.
Scheme 182: Biopathway of synthesis of prostaglandins.
Scheme 183: The reduction and rearrangements of isoprostanes.
Scheme 184: The partial mechanism for linoleate 658 oxidation.
Scheme 185: The transformation of lipid hydroperoxide.
Scheme 186: The acid-catalyzed cleavage of the product from free-radical oxidation of cholesterol (667).
Scheme 187: Two pathways of catechols oxidation.
Scheme 188: Criegee-like or Hock-like rearrangement of the intermediate hydroperoxide 675 in dioxygenase enzyme...
Scheme 189: Carotinoides 679 cleavage by carotenoid cleavage dioxygenases.
Beilstein J. Org. Chem. 2016, 12, 1440–1446, doi:10.3762/bjoc.12.139
Graphical Abstract
Figure 1: Disaccharide repeating unit of the S. pneumoniae serotype 3 CPS.
Figure 2: Building blocks and solid support for the automated solid-phase synthesis of S. pneumoniae serotype...
Scheme 1: Attempted assembly of SP3 trisaccharide 5 using glycosyl phosphate building blocks 1 and 2. Reagent...
Figure 3: HPLC chromatogram of the crude products of the attempted AGA of SP3 trisaccharide 5; conditions: YM...
Scheme 2: Attempted AGA of SP3 trisaccharide 9 using glycosyl phosphate building blocks 1 and 3. Reagents and...
Figure 4: HPLC chromatogram of the crude products of the attempted AGA of SP3 trisaccharide 9; conditions: YM...
Scheme 3: Automated synthesis of linker-bound glucuronic acid 10 using glycosyl phosphate building block 1. R...
Scheme 4: Automated synthesis of SP3 trisaccharide 5 using glycosyl phosphate building blocks 1 and 2. Reagen...
Figure 5: HPLC chromatogram of the crude products of the automated solid-phase SP3 trisaccharide 5 synthesis;...
Scheme 5: Global deprotection of SP3 trisaccharide 5. Reagents and conditions: a) LiOH, H2O2, THF, −5 °C to r...
Beilstein J. Org. Chem. 2016, 12, 670–673, doi:10.3762/bjoc.12.67
Graphical Abstract
Figure 1: 31P NMR spectrum (162 MHz, D2O) of the crude product mixture after refluxing equimolar amounts of t...
Figure 2: IE HPLC trace of the crude product mixture after refluxing equimolar amounts of thymidine and triet...
Figure 3: Possible structures of the most abundant product.
Figure 4: IE HPLC traces of (A) a mixture of tetrameric products, (B) the product mixture after desulfurizati...
Scheme 1: Phosphitylation and subsequent dimerization of thymidine.
Beilstein J. Org. Chem. 2016, 12, 406–412, doi:10.3762/bjoc.12.43
Graphical Abstract
Scheme 1: Synthesis of 3-substituted phospholanes according to earlier data [14-17].
Scheme 2: Synthesis of 3-substituted phospholanes.
Scheme 3: Synthesis of 3-substituted phospholane oxides and sulfides.
Scheme 4: Synthesis of 3-substituted 7a–f and 2-substituted 8a–f phospholanes.
Scheme 5: Synthesis of bisphospholanes.
Scheme 6: Synthesis of bisphospholane-1,1'-oxides and bisphospholane-1,1'-sulfides.
Scheme 7: Synthesis of the molybdenum complex (3-hexyl(benzyl)-1-phenyl(methyl)phospholane)Mo(CO)5.
Scheme 8: Synthesis of molybdenum complexes (1,2(1,6)-bis(1-phenylphospholan-3-yl)ethane(hexane))Mo(CO)5.
Beilstein J. Org. Chem. 2016, 12, 353–361, doi:10.3762/bjoc.12.39
Graphical Abstract
Figure 1: Structures of targeted synthetic inositol derivatives.
Scheme 1: Synthesis of O-alkylated inositol derivatives 1. Reagents and conditions: a) NaBH4, iPrOH, rt, 2 h,...
Scheme 2: Synthesis of O-alkylated fluorinated inositol derivatives 2.
Scheme 3: Synthesis of C-alkenylated inositol intermediates.
Figure 2: nOe correlations for C-alkenylated inositol intermediates.
Scheme 4: Synthesis of C-branched inositol derivatives 3 and 4.
Scheme 5: Synthesis of C-branched fluorinated inositol derivatives 5. Reagents and conditions: a) TrCl, DMAP ...
Scheme 6: Synthesis of C-branched fluorinated inositol derivatives 6. Reagents and conditions: a) TrCl, DMAP ...
Beilstein J. Org. Chem. 2016, 12, 110–116, doi:10.3762/bjoc.12.12
Graphical Abstract
Scheme 1: Oxidation of SF5-anisole and phenol. 19F NMR yields are shown (isolated yields in parentheses).
Scheme 2: Proposed mechanism for the formation of 3 and 4 from SF5 aromatics 1 and 2.
Scheme 3: Oxidation of anisole 10 and phenol 11. 19F NMR yields are given.
Scheme 4: Synthesis of para-benzoquinone 12 and oxidation to maleic acid 4. 19F NMR yields are shown, in pare...
Scheme 5: Catalytic hydrogenation and Diels–Alder reaction of benzoquinone 12.
Figure 1: Optimized geometries of transition states of Diels–Alder reaction of cyclopentadiene with 12. Selec...
Scheme 6: Decomposition of 3 in water.
Scheme 7: Formation of acids 5, 18 and 19 from lactone 3.
Scheme 8: Synthesis of maleic anhydride 20 and Diels–Alder adducts 21.
Scheme 9: Reaction of maleic acid 4 with diazomethane.
Scheme 10: Decarboxylation of maleic acid 4 to acrylic acid 23 in DMSO and the preparation of deuterium labell...
Beilstein J. Org. Chem. 2015, 11, 2166–2170, doi:10.3762/bjoc.11.234
Graphical Abstract
Figure 1: Electrochemical oxidation of 1 in deareated (blue) and O2 saturated (red) solutions of CH2Cl2/0.1 M...
Figure 2: The X-ray structures of compounds 1 and 2.
Figure 3: Decrease of the UV absorption band of compound 1 under irradiation (254 nm) in air-saturated CHCl3, ...
Scheme 1: Photoinduced reaction of 1 in O2 saturated CHCl3 under irradiation by intensive sunlight.
Scheme 2: Heterocycle transformations of 1 in air saturated CHCl3 solutions.
Scheme 3: Proposed mechanism of conversion of oxaziridine 4 to 5.
Figure 4: The X-ray structures of compounds 4 and 5.
Beilstein J. Org. Chem. 2015, 11, 2117–2124, doi:10.3762/bjoc.11.228
Graphical Abstract
Figure 1: Hernandulcin and other bisabolanic derivatives extracted from Lippia dulcis.
Scheme 1: Synthesis of (+)-neoisopulegol. Reagents and conditions: (a) Jones reagent, acetone, 0 °C, 3 h; (b)...
Scheme 2: Reagents and conditions: (a) (i) t-BuOK, BuLi, hexane, −10 °C/rt; 2 h; (ii) BrCH2CH=C(CH3)2; −10°C/...
Scheme 3: Reagents and conditions: (a) cat. methylene blue, light, bubbling O2, CH2Cl2/MeOH 4:1, rt, 15 h; (b...
Scheme 4: Reagents and conditions: (a) (S)-MeCBS or (R)-MeCBS for 15b or 15c, respectively, BH3·Me2S, −78 °C ...
Beilstein J. Org. Chem. 2015, 11, 1274–1331, doi:10.3762/bjoc.11.142
Graphical Abstract
Figure 1: General representation of cyclophanes.
Figure 2: cyclophanes one or more with heteroatom.
Figure 3: Metathesis catalysts 12–17 and C–C coupling catalyst 18.
Figure 4: Natural products containing the cyclophane skeleton.
Figure 5: Turriane family of natural products.
Scheme 1: Synthesis of [3]ferrocenophanes through Mannich reaction. Reagents and conditions: (i) excess HNMe2...
Scheme 2: Synthesis of cyclophanes through Michael addition. Reagents and conditions: (i) xylylene dibromide,...
Scheme 3: Synthesis of normuscopyridine analogue 37 through an oxymercuration–oxidation strategy. Reagents an...
Scheme 4: Synthesis of tribenzocyclotriyne 39 through Castro–Stephens coupling reaction. Reagents and conditi...
Scheme 5: Synthesis of cyclophane 43 through Glaser–Eglinton coupling. Reagents and conditions: (i) 9,10-bis(...
Scheme 6: Synthesis of the macrocyclic C-glycosyl cyclophane through Glaser coupling. Reagents and conditions...
Scheme 7: Synthesis of cyclophane-containing complex 49 through Glaser–Eglinton coupling reaction. Reagents a...
Scheme 8: Synthesis of cyclophane 53 through Glaser–Eglinton coupling. Reagents and conditions: (i) K2CO3, ac...
Figure 6: Cyclophanes 54–56 that have been synthesized through Glaser–Eglinton coupling.
Figure 7: Synthesis of tetrasubstituted [2.2]paracyclophane 57 and chiral cyclophyne 58 through Eglinton coup...
Scheme 9: Synthesis of cyclophane through Glaser–Hay coupling reaction. Reagents and conditions: (i) CuCl2 (1...
Scheme 10: Synthesis of seco-C/D ring analogs of ergot alkaloids through intramolecular Heck reaction. Reagent...
Scheme 11: Synthesis of muscopyridine 73 via Kumada coupling. Reagents and conditions: (i) 72, THF, ether, 20 ...
Scheme 12: Synthesis of the cyclophane 79 via McMurry coupling. Reagents and conditions: (i) 75, decaline, ref...
Scheme 13: Synthesis of stilbenophane 81 via McMurry coupling. Reagents and conditions: (i) TiCl4, Zn, pyridin...
Scheme 14: Synthesis of stilbenophane 85 via McMurry coupling. Reagents and conditions: (i) NBS (2 equiv), ben...
Figure 8: List of cyclophanes prepared via McMurry coupling reaction as a key step.
Scheme 15: Synthesis of paracyclophane by cross coupling involving Pd(0) catalyst. Reagents and conditions: (i...
Scheme 16: Synthesis of the cyclophane 112 via the pinacol coupling and 113 by RCM. Reagents and conditions: (...
Scheme 17: Synthesis of cyclophane derivatives 122a–c via Sonogoshira coupling. Reagents and conditions: (i) C...
Scheme 18: Synthesis of cyclophane 130 via Suzuki–Miyaura reaction as a key step. Reagents and conditions: (i)...
Scheme 19: Synthesis of the mycocyclosin via Suzuki–Miyaura cross coupling. Reagents and conditions: (i) benzy...
Scheme 20: Synthesis of cyclophanes via Wurtz coupling reaction Reagents and conditions: (i) PhLi, Et2O, C6H6,...
Scheme 21: Synthesis of non-natural glycophanes using alkyne metathesis. Reagents and conditions: (i) G-I (12)...
Figure 9: Synthesis of cyclophanes via ring-closing alkyne metathesis.
Scheme 22: Synthesis of crownophanes by cross-enyne metathesis. Reagents and conditions: (i) G-II (13), 5 mol ...
Scheme 23: Synthesis of (−)-cylindrocyclophanes A (156) and (−)-cylindrocyclophanes F (155). Reagents and cond...
Scheme 24: Synthesis of cyclophane 159 derivatives via SM cross-coupling and RCM. Reagents and conditions: (i)...
Scheme 25: Sexithiophene synthesis via cross metathesis. Reagents and conditions: (i) 161, Pd(PPh3)4, K2CO3, T...
Scheme 26: Synthesis of pyrrole-based cyclophane using enyne metathesis. Reagents and conditions: (i) Se, chlo...
Scheme 27: Synthesis of macrocyclic derivatives by RCM. Reagents and conditions: (i) G-I/G-II, CH2Cl2, 0.005 M...
Scheme 28: Synthesis of enantiopure β-lactam-based dienyl bis(dihydrofuran) 179. Reagents and conditions: (i) ...
Scheme 29: Synthesis of a [1.1.6]metaparacyclophane derivative 183 via SM cross coupling. Reagents and conditi...
Scheme 30: Synthesis of a [1.1.6]metaparacyclophane derivative 190 via SM cross coupling. Reagents and conditi...
Scheme 31: Template-promoted synthesis of cyclophanes involving RCM. Reagents and conditions: (i) acenaphthene...
Scheme 32: Synthesis of [3.4]cyclophane derivatives 200 via SM cross coupling and RCM. Reagents and conditions...
Figure 10: Examples for cyclophanes synthesized by RCM.
Scheme 33: Synthesis of the longithorone C framework assisted by fluorinated auxiliaries. Reagents and conditi...
Scheme 34: Synthesis of the longithorone framework via RCM. Reagents and conditions: (i) 213, NaH, THF, rt, 10...
Scheme 35: Synthesis of floresolide B via RCM as a key step. Reagents and conditions: (i) G-II (13, 0.1 equiv)...
Scheme 36: Synthesis of normuscopyridine (223) by the RCM strategy. Reagents and condition: (i) Mg, THF, hexen...
Scheme 37: Synthesis of muscopyridine (73) via RCM. Reagents and conditions: (i) 225, NaH, THF, 0 °C to rt, 1....
Scheme 38: Synthesis of muscopyridine (73) via RCM strategy. Reagents and conditions: (i) NaH, n-BuLi, 5-bromo...
Scheme 39: Synthesis of pyridinophane derivatives 223 and 245. Reagents and conditions: (i) PhSO2Na, TBAB, CH3...
Scheme 40: Synthesis of metacyclophane derivatives 251 and 253. Reagents and conditions: (i) 240, NaH, THF, rt...
Scheme 41: Synthesis of normuscopyridine and its higher analogues. Reagents and conditions: (i) alkenyl bromid...
Scheme 42: Synthesis of fluorinated ferrocenophane 263 via a [2 + 2] cycloaddition. Reagents and conditions: (...
Scheme 43: Synthesis of [2.n]metacyclophanes 270 via a [2 + 2] cycloaddition. Reagents and conditions: (i) Ac2...
Scheme 44: Synthesis of metacyclophane 273 by a [2 + 2 + 2] co-trimerization. Reagents and conditions: (i) [Rh...
Scheme 45: Synthesis of paracyclophane 276 via a [2 + 2 + 2] cycloaddition reaction. Reagents and conditions: ...
Scheme 46: Synthesis of cyclophane 278 via a [2 + 2 + 2] cycloaddition reaction. Reagents and conditions: (i) ...
Scheme 47: Synthesis of cyclophane 280 via a [2 + 2 + 2] cycloaddition. Reagents and conditions: (i) [(Rh(cod)(...
Scheme 48: Synthesis of taxane framework by a [2 + 2 + 2] cycloaddition. Reagents and conditions: (i) Cp(CO)2 ...
Scheme 49: Synthesis of cyclophane 284 and 285 via a [2 + 2 + 2] cycloaddition reaction. Reagents and conditio...
Scheme 50: Synthesis of pyridinophanes 293a,b and 294a,b via a [2 + 2 + 2] cycloaddition. Reagents and conditi...
Scheme 51: Synthesis of pyridinophanes 296 and 297 via a [2 + 2 + 2] cycloaddition. Reagents and conditions: (...
Scheme 52: Synthesis of triazolophane by a 1,3-dipolar cycloaddition. Reagents and conditions: (i) propargyl b...
Scheme 53: Synthesis of glycotriazolophane 309 by a click reaction. Reagents and conditions: (i) LiOH, H2O, Me...
Figure 11: Cyclophanes 310 and 311 prepared via click chemistry.
Scheme 54: Synthesis of cyclophane via the Dötz benzannulation. Reagents and conditions: (i) THF, 100 °C, 12 h...
Scheme 55: Synthesis of [6,6]metacyclophane by a Dötz benzannulation. Reagents and conditions: (i) THF, 100 °C...
Scheme 56: Synthesis of cyclophanes by a Dötz benzannulation. Reagents and conditions: (i) THF, 65 °C, 3 h; (i...
Scheme 57: Synthesis of muscopyridine (73) via an intramolecular DA reaction of ketene. Reagents and condition...
Scheme 58: Synthesis of bis[10]paracyclophane 336 via Diels–Alder reaction. Reagents and conditions: (i) DMAD,...
Scheme 59: Synthesis of [8]paracyclophane via DA reaction. Reagents and conditions: (i) maleic anhydride, 3–5 ...
Scheme 60: Biomimetic synthesis of (−)-longithorone A. Reagents and conditions: (i) Me2AlCl, CH2Cl2, −20 °C, 7...
Scheme 61: Synthesis of sporolide B (349) via a [4 + 2] cycloaddition reaction. Reagents and conditions: (i) P...
Scheme 62: Synthesis of the framework of (+)-cavicularin (352) via a [4 + 2] cycloaddition. Reagents and condi...
Scheme 63: Synthesis of oxazole-containing cyclophane 354 via Beckmann rearrangement. Reagents and conditions:...
Scheme 64: Synthesis of cyclophanes 360a–c via benzidine rearrangement. Reagents and conditions: (i) 356a–d, K2...
Scheme 65: Synthesis of cyclophanes 365a–c via benzidine rearrangement. Reagents and conditions: (i) BocNHNH2,...
Scheme 66: Synthesis of metacyclophane 367 via Ciamician–Dennstedt rearrangement. Reagents and conditions: (i)...
Scheme 67: Synthesis of cyclophane by tandem Claisen rearrangement and RCM as key steps. Reagents and conditio...
Scheme 68: Synthesis of cyclophane derivative 380. Reagents and conditions: (i) K2CO3, CH3CN, allyl bromide, r...
Scheme 69: Synthesis of metacyclophane via Cope rearrangement. Reagents and conditions: (i) MeOH, NaBH4, rt, 1...
Scheme 70: Synthesis of cyclopropanophane via Favorskii rearrangement. Reagents and conditions: (i) Br2, CH2Cl2...
Scheme 71: Cyclophane 389 synthesis via photo-Fries rearrangement. Reagents and conditions: (i) DMAP, EDCl/CHCl...
Scheme 72: Synthesis of normuscopyridine (223) via Schmidt rearrangement. Reagents and conditions: (i) ethyl s...
Scheme 73: Synthesis of crownophanes by tandem Claisen rearrangement. Reagents and conditions: (i) diamine, Et3...
Scheme 74: Attempted synthesis of cyclophanes via tandem Claisen rearrangement and RCM. Reagents and condition...
Scheme 75: Synthesis of muscopyridine via alkylation with 2,6-dimethylpyridine anion. Reagents and conditions:...
Scheme 76: Synthesis of cyclophane via Friedel–Craft acylation. Reagents and conditions: (i) CS2, AlCl3, 7 d, ...
Scheme 77: Pyridinophane 418 synthesis via Friedel–Craft acylation. Reagents and conditions: (i) 416, AlCl3, CH...
Scheme 78: Cyclophane synthesis involving the Kotha–Schölkopf reagent 421. Reagents and conditions: (i) NBS, A...
Scheme 79: Cyclophane synthesis involving the Kotha–Schölkopf reagent 421. Reagents and conditions: (i) BEMP, ...
Scheme 80: Cyclophane synthesis by coupling with TosMIC. Reagents and conditions: (i) (a) ClCH2OCH3, TiCl4, CS2...
Scheme 81: Synthesis of diaza[32]cyclophanes and triaza[33]cyclophanes. Reagents and conditions: (i) DMF, NaH,...
Scheme 82: Synthesis of cyclophane 439 via acyloin condensation. Reagents and conditions: (i) Na, xylene, 75%;...
Scheme 83: Synthesis of multibridged binuclear cyclophane 442 by aldol condensation. Reagents and conditions: ...
Scheme 84: Synthesis of various macrolactones. Reagents and conditions: (i) iPr2EtN, DMF, 77–83%; (ii) TBDMSCl...
Scheme 85: Synthesis of muscone and muscopyridine via Yamaguchi esterification. Reagents and conditions: (i) 4...
Scheme 86: Synthesis of [5]metacyclophane via a double elimination reaction. Reagents and conditions: (i) LiBr...
Figure 12: Cyclophanes 466–472 synthesized via Hofmann elimination.
Scheme 87: Synthesis of cryptophane via Baylis–Hillman reaction. Reagents and conditions: (i) methyl acrylate,...
Scheme 88: Synthesis of cyclophane 479 via double Chichibabin reaction. Reagents and conditions: (i) excess 478...
Scheme 89: Synthesis of cyclophane 483 via double Chichibabin reaction. Reagents and conditions: (i) 481, OH−;...
Scheme 90: Synthesis of cyclopeptide via an intramolecular SNAr reaction. Reagents and conditions: (i) TBAF, T...
Scheme 91: Synthesis of muscopyridine (73) via C-zip ring enlargement reaction. Reagents and conditions: (i) H...
Figure 13: Mechanism of the formation of compound 494.
Scheme 92: Synthesis of indolophanetetraynes 501a,b using the Nicholas reaction as a key step. Reagents and co...
Scheme 93: Synthesis of cyclophane via radical cyclization. Reagents and conditions: (i) cyclododecanone, phen...
Scheme 94: Synthesis of (−)-cylindrocyclophanes A (156) and (−)-cylindrocyclophanes F (155). Reagents and cond...
Scheme 95: Cyclophane synthesis via Wittig reaction. Reagents and conditions: (i) LiOEt (2.1 equiv), THF, −78 ...
Figure 14: Representative examples of cyclophanes synthesized via Wittig reaction.
Scheme 96: Synthesis of the [6]paracyclophane via isomerization of Dewar benzene. Reagents and conditions: (i)...
Beilstein J. Org. Chem. 2015, 11, 1265–1273, doi:10.3762/bjoc.11.141
Graphical Abstract
Scheme 1: One-pot procedure for the preparation of thioesters.
Scheme 2: Reaction of benzoyl chloride, thiourea and butyl acrylate.
Scheme 3: A proposed reaction pathway.