Search for "dicarboxylates" in Full Text gives 31 result(s) in Beilstein Journal of Organic Chemistry.
Beilstein J. Org. Chem. 2025, 21, 1087–1094, doi:10.3762/bjoc.21.86
Graphical Abstract
Figure 1: Oxazolidine-containing bioactive compounds.
Scheme 1: Asymmetric catalytic synthetic methods of oxazolidine derivatives.
Scheme 2: Scope of aziridines and aldehydes.
Scheme 3: Proposed reaction mechanism.
Scheme 4: Gram-scale synthesis.
Beilstein J. Org. Chem. 2025, 21, 884–889, doi:10.3762/bjoc.21.72
Graphical Abstract
Scheme 1: Synthesis of ultracycles.
Figure 1: (a, b) Crystal structure of B4aH (hydrogen atoms are omitted for clarity), and (c) the stacking str...
Figure 2: (a) The structures of host and guests, (b) 1H NMR spectra (298 K, 400 MHz, CD3CN) of B4aH upon titr...
Figure 3: (a–c) DFT-optimized structure of the B4aH-C72− complex. The blue dotted lines represent hydrogen bo...
Beilstein J. Org. Chem. 2024, 20, 3113–3133, doi:10.3762/bjoc.20.258
Graphical Abstract
Figure 1: Example bioactive compounds containing cyclic scaffolds potentially accessible by HVI chemistry.
Figure 2: A general mechanism for HVI-mediated endo- or exo-halocyclisation.
Scheme 1: Metal-free synthesis of β-fluorinated piperidines 6. Ts = tosyl.
Scheme 2: Intramolecular aminofluorination of unactivated alkenes with a palladium catalyst.
Scheme 3: Aminofluorination of alkenes in the synthesis of enantiomerically pure β-fluorinated piperidines. P...
Scheme 4: Synthesis of β-fluorinated piperidines.
Scheme 5: Intramolecular fluoroaminations of unsaturated amines published by Li.
Scheme 6: Intramolecular aminofluorination of unsaturated amines using 1-fluoro-3,3-dimethylbenziodoxole (12)...
Scheme 7: 3-fluoropyrrolidine synthesis. aDiastereomeric ratio (cis/trans) determined by 19F NMR analysis.
Scheme 8: Kitamura’s synthesis of 3-fluoropyrrolidines. Values in parentheses represent the cis:trans ratio.
Scheme 9: Jacobsen’s enantio- and diastereoselective protocol for the synthesis of syn-β-fluoroaziridines 15.
Scheme 10: Different HVI reagents lead to different diastereoselectivity in aminofluorination competing with c...
Scheme 11: Fluorocyclisation of unsaturated alcohols and carboxylic acids to make tetrahydrofurans, fluorometh...
Scheme 12: Oxyfluorination of unsaturated alcohols.
Scheme 13: Synthesis and mechanism of fluoro-benzoxazepines.
Scheme 14: Intramolecular fluorocyclisation of unsaturated carboxylic acids. Yield of isolated product within ...
Scheme 15: Synthesis of fluorinated tetrahydrofurans and butyrolactone.
Scheme 16: Synthesis of fluorinated oxazolines 32. aReaction time increased to 40 hours. Yields refer to isola...
Scheme 17: Electrochemical synthesis of fluorinated oxazolines.
Scheme 18: Electrochemical synthesis of chromanes.
Scheme 19: Synthesis of fluorinated oxazepanes.
Scheme 20: Enantioselective oxy-fluorination with a chiral aryliodide catayst.
Scheme 21: Catalytic synthesis of 5‑fluoro-2-aryloxazolines using BF3·Et2O as a source of fluoride and an acti...
Scheme 22: Intramolecular carbofluorination of alkenes.
Scheme 23: Intramolecular chlorocyclisation of unsaturated amines.
Scheme 24: Synthesis of chlorinated cyclic guanidines 44.
Scheme 25: Synthesis of chlorinated pyrido[2,3-b]indoles 46.
Scheme 26: Chlorolactonization and chloroetherification reactions.
Scheme 27: Proposed mechanism for the synthesis of chloromethyl oxazolines 49.
Scheme 28: Oxychlorination to form oxazine and oxazoline heterocycles promoted by BCl3.
Scheme 29: Aminobromocyclisation of homoallylic sulfonamides 53. The cis:trans ratios based on the 1H NMR of t...
Scheme 30: Synthesis of cyclic imines 45.
Scheme 31: Synthesis of brominated pyrrolo[2,3-b]indoles 59.
Scheme 32: Bromoamidation of alkenes.
Scheme 33: Synthesis of brominated cyclic guanidines 61 and 61’.
Scheme 34: Intramolecular bromocyclisation of N-oxyureas.
Scheme 35: The formation of 3-bromoindoles.
Scheme 36: Bromolactonisation of unsaturated acids 68.
Scheme 37: Synthesis of 5-bromomethyl-2-oxazolines.
Scheme 38: Synthesis of brominated chiral morpholines.
Scheme 39: Bromoenolcyclisation of unsaturated dicarbonyl groups.
Scheme 40: Brominated oxazines and oxazolines with BBr3.
Scheme 41: Synthesis of 5-bromomethtyl-2-phenylthiazoline.
Scheme 42: Intramolecular iodoamination of unsaturated amines.
Scheme 43: Formation of 3-iodoindoles.
Scheme 44: Iodoetherification of 2,2-diphenyl-4-penten-1-carboxylic acid (47’) and 2,2-diphenyl-4-penten-1-ol (...
Scheme 45: Synthesis of 5-iodomethyl-2-oxazolines.
Scheme 46: Synthesis of chiral iodinated morpholines. aFrom the ʟ-form of the amino acid starting material. Th...
Scheme 47: Iodoenolcyclisation of unsaturated dicarbonyl compounds 74.
Scheme 48: Synthesis of 5-iodomethtyl-2-phenylthiazoline (87).
Beilstein J. Org. Chem. 2024, 20, 3007–3015, doi:10.3762/bjoc.20.250
Graphical Abstract
Figure 1: a) Generally desired guest recognition by encapsulation of the analyte within self-assembled metal-...
Scheme 1: Two-synthon approach for ligand preparation via CuAAC click reaction of an azide-functionalized, pr...
Figure 2: Recognition of mono- and dicarboxylates with [L2Zn2] which results in the formation of 1:1 host–gue...
Figure 3: a) Optimized structure (ωB97X‒D4 [83]/def2-SVP [84,85], implicit solvation with DMSO [86], ORCA 5.0.3 [81,82]) of [(C2)@L2...
Figure 4: 1H NMR competition experiments (500 MHz, 500 µM, DMSO-d6, 25 °C) with mixtures of studied analytes ...
Beilstein J. Org. Chem. 2024, 20, 2024–2077, doi:10.3762/bjoc.20.178
Graphical Abstract
Scheme 1: Consecutive three-component synthesis of pyrazoles 1 via in situ-formed 1,3-diketones 2 [44].
Scheme 2: Consecutive three-component synthesis of 4-ethoxycarbonylpyrazoles 5 via SmCl3-catalyzed acylation ...
Scheme 3: Consecutive four-component synthesis of 1-(thiazol-2-yl)pyrazole-3-carboxylates 8 [51].
Scheme 4: Three-component synthesis of thiazolylpyrazoles 17 via in situ formation of acetoacetylcoumarins 18 ...
Scheme 5: Consecutive pseudo-four-component and four-component synthesis of pyrazoles 21 from sodium acetylac...
Scheme 6: Consecutive three-component synthesis of 1-substituted pyrazoles 24 from boronic acids, di(Boc)diim...
Scheme 7: Consecutive three-component synthesis of N-arylpyrazoles 25 via in situ formation of aryl-di(Boc)hy...
Scheme 8: Consecutive three-component synthesis of 1,3,4-substituted pyrazoles 27 and 28 from methylhydrazine...
Scheme 9: Consecutive three-component synthesis of 4-allylpyrazoles 32 via oxidative allylation of 1,3-dicarb...
Scheme 10: Pseudo-five-component synthesis of tris(pyrazolyl)methanes 35 [61].
Scheme 11: Pseudo-three-component synthesis of 5-(indol-3-yl)pyrazoles 39 from 1,3,5-triketones 38 [64].
Scheme 12: Three-component synthesis of thiazolylpyrazoles 43 [65].
Scheme 13: Three-component synthesis of triazolo[3,4-b]-1,3,4-thiadiazin-3-yl substituted 5-aminopyrazoles 47 [67]....
Scheme 14: Consecutive three-component synthesis of 5-aminopyrazoles 49 via formation of β-oxothioamides 50 [68].
Scheme 15: Synthesis of 3,4-biarylpyrazoles 52 from aryl halides, α-bromocinnamaldehyde, and tosylhydrazine vi...
Scheme 16: Consecutive three-component synthesis of 3,4-substituted pyrazoles 57 from iodochromones 55 by Suzu...
Scheme 17: Pseudo-four-component synthesis of pyrazolyl-2-pyrazolines 59 by ring opening/ring closing cyclocon...
Scheme 18: Consecutive three-component synthesis of pyrazoles 61 [77].
Scheme 19: Three-component synthesis of pyrazoles 62 from malononitrile, aldehydes, and hydrazines [78-90].
Scheme 20: Four-component synthesis of pyrano[2,3-c]pyrazoles 63 [91].
Scheme 21: Three-component synthesis of persubstituted pyrazoles 65 from aldehydes, β-ketoesters, and hydrazin...
Scheme 22: Three-component synthesis of pyrazol-4-carbodithioates 67 [100].
Scheme 23: Regioselective three-component synthesis of persubstituted pyrazoles 68 catalyzed by ionic liquid [...
Scheme 24: Consecutive three-component synthesis of 4-halopyrazoles 69 and anellated pyrazoles 70 [102].
Scheme 25: Three-component synthesis of 2,2,2-trifluoroethyl pyrazole-5-carboxylates 72 [103].
Scheme 26: Synthesis of pyrazoles 75 in a one-pot process via carbonylative Heck coupling and subsequent cycli...
Scheme 27: Copper-catalyzed three-component synthesis of 1,3-substituted pyrazoles 76 [105].
Scheme 28: Pseudo-three-component synthesis of bis(pyrazolyl)methanes 78 by ring opening-ring closing cyclocon...
Scheme 29: Three-component synthesis of 1,4,5-substituted pyrazoles 80 [107].
Scheme 30: Consecutive three-component synthesis of 3,5-bis(fluoroalkyl)pyrazoles 83 [111].
Scheme 31: Consecutive three-component synthesis of difluoromethanesulfonyl-functionalized pyrazole 88 [114].
Scheme 32: Consecutive three-component synthesis of perfluoroalkyl-substituted fluoropyrazoles 91 [115].
Scheme 33: Regioselective consecutive three-component synthesis of 1,3,5-substituted pyrazoles 93 [116].
Scheme 34: Three-component synthesis of pyrazoles 96 mediated by trimethyl phosphite [117].
Scheme 35: One-pot synthesis of pyrazoles 99 via Liebeskind–Srogl cross-coupling/cyclocondensation [118].
Scheme 36: Synthesis of 1,3,5-substituted pyrazoles 101 via domino condensation/Suzuki–Miyaura cross-coupling ...
Scheme 37: Consecutive three-component synthesis of 1,3,5-trisubstituted pyrazoles 102 and 103 by Sonogashira ...
Scheme 38: Polymer analogous consecutive three-component synthesis of pyrazole-based polymers 107 [132].
Scheme 39: Synthesis of 1,3,5-substituted pyrazoles 108 by sequentially Pd-catalyzed Kumada–Sonogashira cycloc...
Scheme 40: Consecutive four-step one-pot synthesis of 1,3,4,5-substituted pyrazoles 110 [137].
Scheme 41: Four-component synthesis of pyrazoles 113, 115, and 117 via Sonogashira coupling and subsequent Suz...
Scheme 42: Consecutive four- or five-component synthesis for the preparation of 4-pyrazoly-1,2,3-triazoles 119...
Scheme 43: Four-component synthesis of pyrazoles 121 via alkynone formation by carbonylative Pd-catalyzed coup...
Scheme 44: Preparation of 3-azulenyl pyrazoles 124 by glyoxylation, decarbonylative Sonogashira coupling, and ...
Scheme 45: Four-component synthesis of a 3-indoloylpyrazole 128 [147].
Scheme 46: Two-step synthesis of 5-acylpyrazoles 132 via glyoxylation-Stephen–Castro sequence and subsequent c...
Scheme 47: Copper on iron mediated consecutive three-component synthesis of 3,5-substituted pyrazoles 136 [150].
Scheme 48: Consecutive three-component synthesis of 3-substituted pyrazoles 141 by Sonogashira coupling and su...
Scheme 49: Consecutive three-component synthesis of pyrazoles 143 initiated by Cu(I)-catalyzed carboxylation o...
Scheme 50: Consecutive three-component synthesis of benzamide-substituted pyrazoles 146 starting from N-phthal...
Scheme 51: Consecutive three-component synthesis of 1,3,5-substituted pyrazoles 148 [156].
Scheme 52: Three-component synthesis of 4-ninhydrin-substituted pyrazoles 151 [158].
Scheme 53: Consecutive four-component synthesis of 4-(oxoindol)-1-phenylpyrazole-3-carboxylates 155 [159].
Scheme 54: Three-component synthesis of pyrazoles 160 [160].
Scheme 55: Consecutive three-component synthesis of pyrazoles 165 [162].
Scheme 56: Consecutive three-component synthesis of 3,5-disubstituted and 3-substituted pyrazoles 168 and 169 ...
Scheme 57: Three-component synthesis of 3,4,5-substituted pyrazoles 171 via 1,3-dipolar cycloaddition of vinyl...
Scheme 58: Three-component synthesis of pyrazoles 173 and 174 from aldehydes, tosylhydrazine, and vinylidene c...
Scheme 59: Three-component synthesis of pyrazoles 175 from glyoxyl hydrates, tosylhydrazine, and electron-defi...
Scheme 60: Pseudo-four-component synthesis of pyrazoles 177 from glyoxyl hydrates, tosylhydrazine, and aldehyd...
Scheme 61: Consecutive three-component synthesis of pyrazoles 179 via Knoevenagel-cycloaddition sequence [179].
Scheme 62: Three-component synthesis of 5-dimethylphosphonate substituted pyrazoles 182 from aldehydes, the Be...
Scheme 63: Consecutive three-component synthesis of 5-(dimethyl phosphonate)-substituted pyrazoles 185 from al...
Scheme 64: Three-component synthesis of 5-(dimethyl phosphonate)-substituted pyrazoles 187 from aldehydes, the...
Scheme 65: Three-component synthesis of 5-diethylphosphonate/5-phenylsulfonyl substituted pyrazoles 189 from a...
Scheme 66: Pseudo-three-component synthesis of 3-(dimethyl phosphonate)-substituted pyrazoles 190 [185].
Scheme 67: Three-component synthesis of 3-trifluoromethylpyrazoles 193 [186].
Scheme 68: Consecutive three-component synthesis of 5-stannyl-substituted 4-fluoropyrazole 197 [191,192].
Scheme 69: Pseudo-three-component synthesis of 3,5-diacyl-4-arylpyrazoles 199 [195].
Scheme 70: Three-component synthesis of pyrazoles 204 via nitrilimines [196].
Scheme 71: Three-component synthesis of 1,3,5-substituted pyrazoles 206 via formation of nitrilimines and sali...
Scheme 72: Pseudo four-component synthesis of pyrazoles 209 from acetylene dicarboxylates 147, hydrazonyl chlo...
Scheme 73: Consecutive three-component synthesis of pyrazoles 213 via syndnones 214 [200].
Scheme 74: Consecutive three-component synthesis of pyrazoles 216 via in situ-formed diazomethinimines 217 [201].
Scheme 75: Consecutive three-component synthesis of 3-methylthiopyrazoles 219 from aldehydes, hydrazine, and 1...
Scheme 76: Three-component synthesis of 1,3,5-substituted pyrazoles 220 from aldehydes, hydrazines, and termin...
Scheme 77: Three-component synthesis of 1,3,4,5-substituted pyrazoles 222 from aldehydes, hydrazines, and DMAD ...
Scheme 78: Pseudo three-component synthesis of pyrazoles 224 from sulfonyl hydrazone and benzyl acrylate under...
Scheme 79: Titanium-catalyzed consecutive four-component synthesis of pyrazoles 225 via enamino imines 226 [211]. a...
Scheme 80: Titanium-catalyzed three-component synthesis of pyrazoles 227 via enhydrazino imine complex interme...
Scheme 81: Pseudo-three-component synthesis of pyrazoles 229 via Glaser coupling of terminal alkynes and photo...
Scheme 82: Copper(II)acetate-mediated three-component synthesis of pyrazoles 232 [216].
Scheme 83: Copper-catalyzed three-component synthesis of 1,3,4-substituted pyrazole 234 from oxime acetates, a...
Scheme 84: Three-component synthesis of 3-trifluoroethylpyrazoles 239 [218].
Scheme 85: Pseudo-three-component synthesis of 1,4-bisulfonyl-substituted pyrazoles 242 [219].
Scheme 86: Three-component synthesis of 4-hydroxypyrazole 246 [221].
Beilstein J. Org. Chem. 2024, 20, 859–890, doi:10.3762/bjoc.20.78
Graphical Abstract
Figure 1: Scaffolds commonly reported as bioisosteric replacements of para-substituted benzene and examples p...
Figure 2: 1,2-BCPs as isosteres for ortho-and meta-substituted benzenes: comparison of reported exit vector p...
Scheme 1: 1,2-Disubstituted bicyclo[1.1.1]pentanes as isosteres of ortho-substituted benzenes. A: Baran, Coll...
Scheme 2: Synthesis of 1,2-BCPs from BCP 15 by bridge C–H bromination as reported by MacMillan and co-workers ...
Figure 3: Comparative physicochemical data of telmisartan, lomitapide and their BCP isosteres [26,33]. Shake flask d...
Figure 4: 1,2-Disubstituted bicyclo[2.1.1]hexanes as isosteres of ortho-benzenes: Exit vector parameters of t...
Scheme 3: Synthesis of 1,2-disubstituted bicyclo[2.1.1]hexanes via alkene insertion into bicyclo[1.1.0]butane...
Scheme 4: Synthesis of 1,2-disubstituted bicyclo[2.1.1]hexanes via intramolecular crossed [2 + 2] cycloadditi...
Figure 5: Comparison of physicochemical data of fluxapyroxad and boscalid and their 1,2-BCH bioisosteres [36]. Sh...
Figure 6: Antifungal activity of fluxapyroxad, its 1,5-BCH bioisostere (±)-55, boscalid and its bioisostere 1...
Figure 7: 1,5-Disubstituted bicyclo[2.1.1]hexanes as isosteres of ortho-substituted benzenes. Comparison of e...
Scheme 5: Synthesis of 1,5-disubstituted bicyclo[2.1.1]hexanes as isosteres of ortho-benzenes via intramolecu...
Figure 8: Comparison of physicochemical data of fluxapyroxad and boscalid and their 1,5-BCH bioisosteres [45]. Sh...
Figure 9: Antifungal activity of fluxapyroxad, its 1,5-BCH bioisostere (±)-64, boscalid and its bioisostere 1...
Figure 10: 1,5-Disubstituted 3-oxabicylco[2.1.1]hexanes as isosteres for ortho-benzenes: Comparison of exit ve...
Scheme 6: Synthesis of 1,5-disubstituted 3-oxabicyclo[2.1.1]hexanes as isosteres for ortho-benzenes via intra...
Figure 11: Comparison of physicochemical data of fluxapyroxad and boscalid and their 3-oxa-1,5-BCH bioisostere...
Figure 12: Antifungal activity of fluxapyroxad and boscalid and their 3-oxa-1,5-BCH bioisosteres (±)-75 and (±...
Figure 13: 1,2-Disubstituted bicyclo[3.1.1]heptanes as isosteres of ortho-benzenes. Schematic representation o...
Scheme 7: Synthesis of 1,2-disubstituted bicyclo[3.1.1]heptanes as isosteres for ortho-benzenes via alkene in...
Figure 14: 1,2-Disubstituted stellanes as ortho-benzene isosteres: Comparison of selected exit vector paramete...
Scheme 8: Synthesis of 1,2-disubstituted stellanes as isosteres for ortho-benzenes reported by Ryabukhin, Vol...
Figure 15: 1,2-Disubstituted cubanes as ortho-benzene isosteres: Comparison of substituent distances and angle...
Scheme 9: Synthesis of 1,2-disubsituted cubanes as isosteres for ortho-benzenes. A: Synthesis of 1,2-cubane d...
Figure 16: 1,3-Disubstituted bicyclo[2.1.1]hexanes as isosteres of meta-benzenes: comparative exit vector para...
Scheme 10: Synthesis of 1,3-disubstituted bicyclo[2.1.1]hexanes as isosteres for meta-benzenes reported by Wal...
Figure 17: 1,4-Disubstituted bicyclo[2.1.1]hexanes as isosteres of meta-benzenes: comparative exit vector para...
Scheme 11: Synthesis of 1,4-disubstituted bicyclo[2.1.1}hexanes as isosteres for ortho-benzenes via intramolec...
Figure 18: 1,4-Disubstituted-2-oxabicyclo[2.1.1]hexanes as meta-benzene isosteres: comparison of selected exit...
Scheme 12: Synthesis of 1,4-disubstituted 2-oxabicyclo[2.1.1]hexanes as isosteres for meta-benzenes. A: Mykhai...
Figure 19: Comparative physicochemical data for 2- and 3-oxa-1,4-BCHs and para-substituted benzene equivalents...
Figure 20: 1,5-Disubstituted bicyclo[3.1.1]heptanes as isosteres of meta-benzenes: comparison of exit vector p...
Scheme 13: Synthesis of [3.1.1]propellane as a precursor for 1,5-disubsituted bicyclo[3.1.1]heptanes. A: aGass...
Scheme 14: Synthesis of iodine-substituted 1,5-disubstituted bicyclo[3.1.1]heptanes as isosteres for meta-benz...
Scheme 15: Synthesis of nitrogen-, chalcogen- and tin-substituted 1,5-disubstituted bicyclo[3.1.1]heptanes as ...
Figure 21: Comparative physicochemical data of URB597 and 1,5-BCHep isostere 146 [27]. Kinetic aqueous solubility ...
Figure 22: [2]-Ladderanes as isosteres of meta-benzenes: comparison of reported exit vector parameters [63].
Scheme 16: Synthesis of cis-2,6-disubstituted bicyclo[2.2.0]hexanes as isosteres for meta-benzenes. A: Brown a...
Figure 23: Comparative physicochemical data of meta-benzene 158 and [2]-ladderane isostere 159 [63]. Partition coe...
Figure 24: 1,3-Disubstituted cubanes as isosteres of meta-benzenes: comparison of selected exit vector paramet...
Scheme 17: Synthesis of 1,3-disubsituted cubanes as isosteres for meta-benzenes. A: MacMillan and co-workers’ ...
Figure 25: Comparative physicochemical data of lumacaftor and its 1,3-cubane bioisostere 183 [51]. Distribution co...
Figure 26: 1,3-Disubstituted cuneanes as isosteres of meta-benzenes: comparison of selected exit vector parame...
Scheme 18: Synthesis of 1,3-cuneanes as isosteres of meta-benzene. A: Synthesis of 1,3-cuneanes reported by La...
Figure 27: Comparative physicochemical data of sonidegib and its 1,3-cuneane isostere 190 [71]. aSolubility was to...
Figure 28: Exemplary polysubstituted scaffolds related to disubstituted scaffolds suggested as isosteres of or...
Beilstein J. Org. Chem. 2023, 19, 1471–1502, doi:10.3762/bjoc.19.106
Graphical Abstract
Scheme 1: Sulfur-containing bioactive molecules.
Scheme 2: Scandium-catalyzed synthesis of thiosulfonates.
Scheme 3: Palladium-catalyzed aryl(alkyl)thiolation of unactivated arenes.
Scheme 4: Catalytic cycle for Pd-catalyzed aryl(alkyl)thiolation of unactivated arenes.
Scheme 5: Iron- or boron-catalyzed C–H arylthiation of substituted phenols.
Scheme 6: Iron-catalyzed azidoalkylthiation of alkenes.
Scheme 7: Plausible mechanism for iron-catalyzed azidoalkylthiation of alkenes.
Scheme 8: BF3·Et2O‑mediated electrophilic cyclization of aryl alkynoates.
Scheme 9: Tentative mechanism for BF3·Et2O‑mediated electrophilic cyclization of aryl alkynoates.
Scheme 10: Construction of 6-substituted benzo[b]thiophenes.
Scheme 11: Plausible mechanism for construction of 6-substituted benzo[b]thiophenes.
Scheme 12: AlCl3‑catalyzed cyclization of N‑arylpropynamides with N‑sulfanylsuccinimides.
Scheme 13: Synthetic utility of AlCl3‑catalyzed cyclization of N‑arylpropynamides with N‑sulfanylsuccinimides.
Scheme 14: Sulfenoamination of alkenes with sulfonamides and N-sulfanylsuccinimides.
Scheme 15: Lewis acid/Brønsted acid controlled Pd-catalyzed functionalization of aryl C(sp2)–H bonds.
Scheme 16: Possible mechanism for Lewis acid/Brønsted acid controlled Pd-catalyzed functionalization of aryl C...
Scheme 17: FeCl3-catalyzed carbosulfenylation of unactivated alkenes.
Scheme 18: Copper-catalyzed electrophilic thiolation of organozinc halides.
Scheme 19: h-BN@Copper(II) nanomaterial catalyzed cross-coupling reaction of sulfoximines and N‑(arylthio)succ...
Scheme 20: AlCl3‑mediated cyclization and sulfenylation of 2‑alkyn-1-one O‑methyloximes.
Scheme 21: Lewis acid-promoted 2-substituted cyclopropane 1,1-dicarboxylates with sulfonamides and N-(arylthio...
Scheme 22: Lewis acid-mediated cyclization of β,γ-unsaturated oximes and hydrazones with N-(arylthio/seleno)su...
Scheme 23: Credible pathway for Lewis acid-mediated cyclization of β,γ-unsaturated oximes with N-(arylthio)suc...
Scheme 24: Synthesis of 4-chalcogenyl pyrazoles via chalcogenation/cyclization of α,β-alkynic hydrazones.
Scheme 25: Controllable synthesis of 3-thiolated pyrroles and pyrrolines.
Scheme 26: Possible mechanism for controllable synthesis of 3-thiolated pyrroles and pyrrolines.
Scheme 27: Co-catalyzed C2-sulfenylation and C2,C3-disulfenylation of indole derivatives.
Scheme 28: Plausible catalytic cycle for Co-catalyzed C2-sulfenylation and C2,C3-disulfenylation of indoles.
Scheme 29: C–H thioarylation of electron-rich arenes by iron(III) triflimide catalysis.
Scheme 30: Difunctionalization of alkynyl bromides with thiosulfonates and N-arylthio succinimides.·
Scheme 31: Suggested mechanism for difunctionalization of alkynyl bromides with thiosulfonates and N-arylthio ...
Scheme 32: Synthesis of thioesters, acyl disulfides, ketones, and amides by N-thiohydroxy succinimide esters.
Scheme 33: Proposed mechanism for metal-catalyzed selective acylation and acylthiolation.
Scheme 34: AlCl3-catalyzed synthesis of 3,4-bisthiolated pyrroles.
Scheme 35: α-Sulfenylation of aldehydes and ketones.
Scheme 36: Acid-catalyzed sulfetherification of unsaturated alcohols.
Scheme 37: Enantioselective sulfenylation of β-keto phosphonates.
Scheme 38: Organocatalyzed sulfenylation of 3‑substituted oxindoles.
Scheme 39: Sulfenylation and chlorination of β-ketoesters.
Scheme 40: Intramolecular sulfenoamination of olefins.
Scheme 41: Plausible mechanism for intramolecular sulfenoamination of olefins.
Scheme 42: α-Sulfenylation of 5H-oxazol-4-ones.
Scheme 43: Metal-free C–H sulfenylation of electron-rich arenes.
Scheme 44: TFA-promoted C–H sulfenylation indoles.
Scheme 45: Proposed mechanism for TFA-promoted C–H sulfenylation indoles.
Scheme 46: Organocatalyzed sulfenylation and selenenylation of 3-pyrrolyloxindoles.
Scheme 47: Organocatalyzed sulfenylation of S-based nucleophiles.
Scheme 48: Conjugate Lewis base Brønsted acid-catalyzed sulfenylation of N-heterocycles.
Scheme 49: Mechanism for activation of N-sulfanylsuccinimide by conjugate Lewis base Brønsted acid catalyst.
Scheme 50: Sulfenylation of deconjugated butyrolactams.
Scheme 51: Intramolecular sulfenofunctionalization of alkenes with phenols.
Scheme 52: Organocatalytic 1,3-difunctionalizations of Morita–Baylis–Hillman carbonates.
Scheme 53: Organocatalytic sulfenylation of β‑naphthols.
Scheme 54: Acid-promoted oxychalcogenation of o‑vinylanilides with N‑(arylthio/arylseleno)succinimides.
Scheme 55: Lewis base/Brønsted acid dual-catalytic C–H sulfenylation of aryls.
Scheme 56: Lewis base-catalyzed sulfenoamidation of alkenes.
Scheme 57: Cyclization of allylic amide using a Brønsted acid and tetrabutylammonium chloride.
Scheme 58: Catalytic electrophilic thiocarbocyclization of allenes with N-thiosuccinimides.
Scheme 59: Suggested mechanism for electrophilic thiocarbocyclization of allenes with N-thiosuccinimides.
Scheme 60: Chiral chalcogenide-catalyzed enantioselective hydrothiolation of alkenes.
Scheme 61: Proposed mechanism for chalcogenide-catalyzed enantioselective hydrothiolation of alkenes.
Scheme 62: Organocatalytic sulfenylation for synthesis a diheteroatom-bearing tetrasubstituted carbon centre.
Scheme 63: Thiolative cyclization of yne-ynamides.
Scheme 64: Synthesis of alkynyl and acyl disulfides from reaction of thiols with N-alkynylthio phthalimides.
Scheme 65: Oxysulfenylation of alkenes with 1-(arylthio)pyrrolidine-2,5-diones and alcohols.
Scheme 66: Arylthiolation of arylamines with (arylthio)-pyrrolidine-2,5-diones.
Scheme 67: Catalyst-free isothiocyanatoalkylthiation of styrenes.
Scheme 68: Sulfenylation of (E)-β-chlorovinyl ketones toward 3,4-dimercaptofurans.
Scheme 69: HCl-promoted intermolecular 1, 2-thiofunctionalization of aromatic alkenes.
Scheme 70: Possible mechanism for HCl-promoted 1,2-thiofunctionalization of aromatic alkenes.
Scheme 71: Coupling reaction of diazo compounds with N-sulfenylsuccinimides.
Scheme 72: Multicomponent reactions of disulfides with isocyanides and other nucleophiles.
Scheme 73: α-Sulfenylation and β-sulfenylation of α,β-unsaturated carbonyl compounds.
Beilstein J. Org. Chem. 2023, 19, 982–990, doi:10.3762/bjoc.19.73
Graphical Abstract
Scheme 1: Various cycloaddition reactions of 5,6-unsymmetric 1,4-dihydropyridines.
Figure 1: Single crystal structure of the compound 4k.
Figure 2: Single crystal structure of compound 5a.
Figure 3: Single crystal structure of compound 6f.
Scheme 2: Plausible reaction mechanism for the various products 4, 5, and 6.
Beilstein J. Org. Chem. 2022, 18, 991–998, doi:10.3762/bjoc.18.99
Graphical Abstract
Scheme 1: Representative cycloaddition reactions of phenacylmalononitriles.
Figure 1: Single crystal structure of compound 3k.
Figure 2: Single crystal structure of compound 4a.
Figure 3: Single crystal structure of compound 4c.
Scheme 2: Proposed reaction mechanism for compounds 3, 4, and 5.
Figure 4: Single crystal structure of compound 5.
Scheme 3: Control experiment.
Beilstein J. Org. Chem. 2021, 17, 2028–2050, doi:10.3762/bjoc.17.131
Graphical Abstract
Figure 1: Examples of anthracene derivatives and their applications.
Scheme 1: Rhodium-catalyzed oxidative coupling reactions of arylboronic acids with internal alkynes.
Scheme 2: Rhodium-catalyzed oxidative benzannulation reactions of 1-adamantoyl-1-naphthylamines with internal...
Scheme 3: Gold/bismuth-catalyzed cyclization of o-alkynyldiarylmethanes.
Scheme 4: [2 + 2 + 2] Cyclotrimerization reactions with alkynes/nitriles in the presence of nickel and cobalt...
Scheme 5: Cobalt-catalyzed [2 + 2 + 2] cyclotrimerization reactions with bis(trimethylsilyl)acetylene (23).
Scheme 6: [2 + 2 + 2] Alkyne-cyclotrimerization reactions catalyzed by a CoCl2·6H2O/Zn reagent.
Scheme 7: Pd(II)-catalyzed sp3 C–H alkenylation of diphenyl carboxylic acids with acrylates.
Scheme 8: Pd(II)-catalyzed sp3 C–H arylation with o-tolualdehydes and aryl iodides.
Scheme 9: Alkylation of arenes with aromatic aldehydes in the presence of acetyl bromide and ZnBr2/SiO2.
Scheme 10: BF3·H2O-catalyzed hydroxyalkylation of arenes with aromatic dialdehyde 44.
Scheme 11: Bi(OTf)3-promoted Friedel–Crafts alkylation of triarylmethanes and aromatic acylals and of arenes a...
Scheme 12: Reduction of anthraquinones by using Zn/pyridine or Zn/NaOH reductive methods.
Scheme 13: Two-step route to novel substituted Indenoanthracenes.
Scheme 14: Synthesis of 1,8-diarylanthracenes through Suzuki–Miyaura coupling reaction in the presence of Pd-P...
Scheme 15: Synthesis of five new substituted anthracenes by using LAH as reducing agent.
Scheme 16: One-pot procedure to synthesize substituted 9,10-dicyanoanthracenes.
Scheme 17: Reduction of bromoanthraquinones with NaBH4 in alkaline medium.
Scheme 18: In(III)-catalyzed reductive-dehydration intramolecular cycloaromatization of 2-benzylic aromatic al...
Scheme 19: Acid-catalyzed cyclization of new O-protected ortho-acetal diarylmethanols.
Scheme 20: Lewis acid-mediated regioselective cyclization of asymmetric diarylmethine dipivalates and diarylme...
Scheme 21: BF3·OEt2/CF3SO3H-mediated cyclodehydration reactions of 2-(arylmethyl)benzaldehydes and 2-(arylmeth...
Scheme 22: Synthesis of 2,3,6,7-anthracenetetracarbonitrile (90) by double Wittig reaction followed by deprote...
Scheme 23: Homo-elongation protocol for the synthesis of substituted acene diesters/dinitriles.
Scheme 24: Synthesis of two new parental BN anthracenes via borylative cyclization.
Scheme 25: Synthesis of substituted anthracenes from a bifunctional organomagnesium alkoxide.
Scheme 26: Palladium-catalyzed tandem C–H activation/bis-cyclization of propargylic carbonates.
Scheme 27: Ruthenium-catalyzed C–H arylation of acetophenone derivatives with arenediboronates.
Scheme 28: Pd-catalyzed intramolecular cyclization of (Z,Z)-p-styrylstilbene derivatives.
Scheme 29: AuCl-catalyzed double cyclization of diiodoethynylterphenyl compounds.
Scheme 30: Iodonium-induced electrophilic cyclization of terphenyl derivatives.
Scheme 31: Oxidative photocyclization of 1,3-distyrylbenzene derivatives.
Scheme 32: Oxidative cyclization of 2,3-diphenylnaphthalenes.
Scheme 33: Suzuki-Miyaura/isomerization/ring closing metathesis strategy to synthesize benz[a]anthracenes.
Scheme 34: Green synthesis of oxa-aza-benzo[a]anthracene and oxa-aza-phenanthrene derivatives.
Scheme 35: Triple benzannulation of substituted naphtalene via a 1,3,6-naphthotriyne synthetic equivalent.
Scheme 36: Zinc iodide-catalyzed Diels–Alder reactions with 1,3-dienes and aroyl propiolates followed by intra...
Scheme 37: H3PO4-promoted intramolecular cyclization of substituted benzoic acids.
Scheme 38: Palladium-catalyzed intermolecular direct acylation of aromatic aldehydes and o-iodoesters.
Scheme 39: Cycloaddition/oxidative aromatization of quinone and β-enamino esters.
Scheme 40: ʟ-Proline-catalyzed [4 + 2] cycloaddition reaction of naphthoquinones and α,β-unsaturated aldehydes....
Scheme 41: Iridium-catalyzed [2 + 2 + 2] cycloaddition of a 1,2-bis(propiolyl)benzene derivative with alkynes.
Scheme 42: Synthesis of several anthraquinone derivatives by using InCl3 and molecular iodine.
Scheme 43: Indium-catalyzed multicomponent reactions employing 2-hydroxy-1,4-naphthoquinone (186), β-naphthol (...
Scheme 44: Synthesis of substituted anthraquinones catalyzed by an AlCl3/MeSO3H system.
Scheme 45: Palladium(II)-catalyzed/visible light-mediated synthesis of anthraquinones.
Scheme 46: [4 + 2] Anionic annulation reaction for the synthesis of substituted anthraquinones.
Beilstein J. Org. Chem. 2020, 16, 2687–2700, doi:10.3762/bjoc.16.219
Graphical Abstract
Figure 1: Schematic illustration of the analyte-induced crosslinking of gold nanoparticles containing a mixtu...
Scheme 1: Syntheses of the ligands rac-1 and (R)-1. Conditions: i) TsCl, NaOH, THF, 0 °C, 60 min → 25 °C, 80 ...
Scheme 2: Synthesis of ligand 2. Conditions: i) potassium phthalimide, DMF, 25 °C, 18 h, 67%; ii) 2,2'-dipico...
Figure 2: Photographs of solutions of NPrac-1 in water (0.25 mg/mL) containing different sodium salts at a co...
Figure 3: Sections of the 1H NMR spectra of solutions of NP25 in D2O/CD3OD 1:2 (v/v) between 8.9 and 3.9 ppm ...
Figure 4: Images of vials containing solutions of NP10-Zn (0.25 mg/mL) in water/methanol 1:2 (v/v) and additi...
Figure 5: Photograph of the solutions of the competition experiment. Vial (a) only contained NP10-Zn (and the...
Figure 6: UV–vis spectra of NP10-Zn (0.25 mg/mL in the initial measurement) in water/methanol 1:2 (v/v) conta...
Figure 7: TEM images of NP10-Zn (0.25 mg/mL) in water/methanol 1:2 (v/v) before (a) and after the addition of...
Beilstein J. Org. Chem. 2020, 16, 1418–1435, doi:10.3762/bjoc.16.118
Graphical Abstract
Scheme 1: [3 + 2] cyclization catalyzed by diaryl disulfide.
Scheme 2: [3 + 2] cycloaddition catalyzed by disulfide.
Scheme 3: Disulfide-bridged peptide-catalyzed enantioselective cycloaddition.
Scheme 4: Disulfide-catalyzed [3 + 2] methylenecyclopentane annulations.
Scheme 5: Disulfide as a HAT cocatalyst in the [4 + 2] cycloaddition reaction.
Scheme 6: Proposed mechanism of the [4 + 2] cycloaddition reaction using disulfide as a HAT cocatalyst.
Scheme 7: Disulfide-catalyzed ring expansion of vinyl spiro epoxides.
Scheme 8: Disulfide-catalyzed aerobic oxidation of diarylacetylene.
Scheme 9: Disulfide-catalyzed aerobic photooxidative cleavage of olefins.
Scheme 10: Disulfide-catalyzed aerobic oxidation of 1,3-dicarbonyl compounds.
Scheme 11: Proposed mechanism of the disulfide-catalyzed aerobic oxidation of 1,3-dicarbonyl compounds.
Scheme 12: Disulfide-catalyzed oxidation of allyl alcohols.
Scheme 13: Disulfide-catalyzed diboration of alkynes.
Scheme 14: Dehalogenative radical cyclization catalyzed by disulfide.
Scheme 15: Hydrodifluoroacetamidation of alkenes catalyzed by disulfide.
Scheme 16: Plausible mechanism of the hydrodifluoroacetamidation of alkenes catalyzed by disulfide.
Scheme 17: Disulfide-cocatalyzed anti-Markovnikov olefin hydration reactions.
Scheme 18: Disulfide-catalyzed decarboxylation of carboxylic acids.
Scheme 19: Proposed mechanism of the disulfide-catalyzed decarboxylation of carboxylic acids.
Scheme 20: Disulfide-catalyzed decarboxylation of carboxylic acids.
Scheme 21: Disulfide-catalyzed conversion of maleate esters to fumarates and 5H-furanones.
Scheme 22: Disulfide-catalyzed isomerization of difluorotriethylsilylethylene.
Scheme 23: Disulfide-catalyzed isomerization of allyl alcohols to carbonyl compounds.
Scheme 24: Proposed mechanism for the disulfide-catalyzed isomerization of allyl alcohols to carbonyl compound...
Scheme 25: Diphenyl disulfide-catalyzed enantioselective synthesis of ophirin B.
Scheme 26: Disulfide-catalyzed isomerization in the total synthesis of (+)-hitachimycin.
Scheme 27: Disulfide-catalyzed isomerization in the synthesis of (−)-gloeosporone.
Beilstein J. Org. Chem. 2020, 16, 1357–1410, doi:10.3762/bjoc.16.116
Graphical Abstract
Figure 1: Examples of biologically active thietane-containing molecules.
Figure 2: The diverse methods for the synthesis of thietanes.
Scheme 1: Synthesis of 1-(thietan-2-yl)ethan-1-ol (10) from 3,5-dichloropentan-2-ol (9).
Scheme 2: Synthesis of thietanose nucleosides 2,14 from 2,2-bis(bromomethyl)propane-1,3-diol (11).
Scheme 3: Synthesis of methyl 3-vinylthietane-3-carboxylate (19).
Scheme 4: Synthesis of 1,6-thiazaspiro[3.3]heptane (24).
Scheme 5: Synthesis of 6-amino-2-thiaspiro[3.3]heptane hydrochloride (28).
Scheme 6: Synthesis of optically active thietane 31 from vitamin C.
Scheme 7: Synthesis of an optically active thietane nucleoside from diethyl L-tartrate (32).
Scheme 8: Synthesis of thietane-containing spironucleoside 40 from 5-aldo-3-O-benzyl-1,2-O-isopropylidene-α-D...
Scheme 9: Synthesis of optically active 2-methylthietane-containing spironucleoside 43.
Scheme 10: Synthesis of a double-linked thietane-containing spironucleoside 48.
Scheme 11: Synthesis of two diastereomeric thietanose nucleosides via 2,4-di(benzyloxymethyl)thietane (49).
Scheme 12: Synthesis of the thietane-containing PI3k inhibitor candidate 54.
Scheme 13: Synthesis of the spirothietane 57 as the key intermediate to Nuphar sesquiterpene thioalkaloids.
Scheme 14: Synthesis of spirothietane 61 through a direct cyclic thioetherification of 3-mercaptopropan-1-ol.
Scheme 15: Synthesis of thietanes 66 from 1,3-diols 62.
Scheme 16: Synthesis of thietanylbenzimidazolone 75 from (iodomethyl)thiazolobenzimidazole 70.
Scheme 17: Synthesis of 2-oxa-6-thiaspiro[3.3]heptane (80) from bis(chloromethyl)oxetane 76 and thiourea.
Scheme 18: Synthesis of the thietane-containing glycoside, 2-O-p-toluenesulfonyl-4,6-thioanhydro-α-D-gulopyran...
Scheme 19: Synthesis of methyl 4,6-thioanhydro-α-D-glucopyranoside (89).
Scheme 20: Synthesis of thietane-fused α-D-galactopyranoside 93.
Scheme 21: Synthesis of thietane-fused α-D-gulopyranoside 100.
Scheme 22: Synthesis of 3,5-anhydro-3-thiopentofuranosides 104.
Scheme 23: Synthesis of anhydro-thiohexofuranosides 110, 112 and 113 from from 1,2:4,5-di-O-isopropylidene D-f...
Scheme 24: Synthesis of optically active thietanose nucleosides from D- and L-xyloses.
Scheme 25: Synthesis of thietane-fused nucleosides.
Scheme 26: Synthesis of 3,5-anhydro-3-thiopentofuranosides.
Scheme 27: Synthesis of 2-amino-3,5-anhydro-3-thiofuranoside 141.
Scheme 28: Synthesis of thietane-3-ols 145 from (1-chloromethyl)oxiranes 142 and hydrogen sulfide.
Scheme 29: Synthesis of thietane-3-ol 145a from chloromethyloxirane (142a).
Scheme 30: Synthesis of thietane-3-ols 145 from 2-(1-haloalkyl)oxiranes 142 and 147 with ammonium monothiocarb...
Scheme 31: Synthesis of 7-deoxy-5(20)thiapaclitaxel 154a, a thietane derivative of taxoids.
Scheme 32: Synthesis of 5(20)-thiadocetaxel 158 from 10-deacetylbaccatin III (155).
Scheme 33: Synthesis of thietane derivatives 162 as precursors for deoxythiataxoid synthesis through oxiraneme...
Scheme 34: Synthesis of 7-deoxy 5(20)-thiadocetaxel 154b.
Scheme 35: Mechanism for the formation of the thietane ring in 171 from oxiranes with vicinal leaving groups 1...
Scheme 36: Synthesis of cis-2,3-disubstituted thietane 175 from thiirane-2-methanol 172.
Scheme 37: Synthesis of a bridged thietane 183 from aziridine cyclohexyl tosylate 179 and ammonium tetrathiomo...
Scheme 38: Synthesis of thietanes via the photochemical [2 + 2] cycloaddition of thiobenzophenone 184a with va...
Scheme 39: Synthesis of spirothietanes through the photo [2 + 2] cycloaddition of cyclic thiocarbonyls with ol...
Scheme 40: Photochemical synthesis of spirothietane-thioxanthenes 210 from thioxanthenethione (208) and butatr...
Scheme 41: Synthesis of thietanes 213 from 2,4,6-tri(tert-butyl)thiobenzaldehyde (211) with substituted allene...
Scheme 42: Photochemical synthesis of spirothietanes 216 and 217 from N-methylthiophthalimide (214) with olefi...
Scheme 43: Synthesis of fused thietanes from quadricyclane with thiocarbonyl derivatives 219.
Scheme 44: Synthesis of tricyclic thietanes via the photo [2 + 2] cycloaddition of N-methyldithiosuccinimides ...
Scheme 45: Synthesis of tricyclic thietanes via the photo [2 + 2] cycloaddition of N-methylthiosuccinimide/thi...
Scheme 46: Synthesis of tricyclic thietanes via the photo [2 + 2] cycloaddition of N-alkylmonothiophthalimides...
Scheme 47: Synthesis of spirothietanes from dithiosuccinimides 223 with 2,3-dimethyl-2-butene (215a).
Scheme 48: Synthesis of thietanes 248a,b from diaryl thione 184b and ketene acetals 247a,b.
Scheme 49: Photocycloadditions of acridine-9-thiones 249 and pyridine-4(1H)-thione (250) with 2-methylacrynitr...
Scheme 50: Synthesis of thietanes via the photo [2 + 2] cycloaddition of mono-, di-, and trithiobarbiturates 2...
Scheme 51: Synthesis of spirothietanes via the photo [2 + 2] cycloaddition of 1,1,3-trimethyl-2-thioxo-1,2-dih...
Scheme 52: Synthesis of spirothietanes via the photo [2 + 2] cycloaddition of thiocoumarin 286 with olefins.
Scheme 53: Photochemical synthesis of thietanes 296–299 from semicyclic and acyclic thioimides 292–295 and 2,3...
Scheme 54: Photochemical synthesis of spirothietane 301 from 1,3,3-trimethylindoline-2-thione (300) and isobut...
Scheme 55: Synthesis of spirobenzoxazolethietanes 303 via the photo [2 + 2] cycloaddition of alkyl and aryl 2-...
Scheme 56: Synthesis of spirothietanes from tetrahydrothioxoisoquinolines 306 and 307 with olefins.
Scheme 57: Synthesis of spirothietanes from 1,3-dihydroisobenzofuran-1-thiones 311 and benzothiophene-1-thione...
Scheme 58: Synthesis of 2-triphenylsilylthietanes from phenyl triphenylsilyl thioketone (316) with electron-po...
Scheme 59: Diastereoselective synthesis of spiropyrrolidinonethietanes 320 via the photo [2 + 2] cycloaddition...
Scheme 60: Synthesis of bicyclic thietane 323 via the photo [2 + 2] cycloaddition of 2,4-dioxo-3,4-dihydropyri...
Scheme 61: Photo-induced synthesis of fused thietane-2-thiones 325 and 326 from silacyclopentadiene 324 and ca...
Scheme 62: Synthesis of highly strained tricyclic thietanes 328 via the intramolecular photo [2 + 2] cycloaddi...
Scheme 63: Synthesis of tri- and pentacyclic thietanes 330 and 332, respectively, through the intramolecular p...
Scheme 64: Synthesis of tricyclic thietanes 334 via the intramolecular photo [2 + 2] cycloaddition of N-vinylt...
Scheme 65: Synthesis of tricyclic thietanes 336 via the intramolecular photo [2 + 2] cycloaddition of N-but-3-...
Scheme 66: Synthesis of tricyclic thietanes via the intramolecular photo [2 + 2] cycloaddition of N-but-3-enyl...
Scheme 67: Synthesis of tetracyclic thietane 344 through the intramolecular photo [2 + 2] cycloaddition of N-[...
Scheme 68: Synthesis of tri- and tetracyclic thietanes 348, 350, and 351, through the intramolecular photo [2 ...
Scheme 69: Synthesis of tetracyclic fused thietane 354 via the photo [2 + 2] cycloaddition of vinyl 2-thioxo-3H...
Scheme 70: Synthesis of highly rigid thietane-fused β-lactams via the intramolecular photo [2 + 2] cycloadditi...
Scheme 71: Asymmetric synthesis of a highly rigid thietane-fused β-lactam 356a via the intramolecular photo [2...
Scheme 72: Diastereoselective synthesis of the thietane-fused β-lactams via the intramolecular photo [2 + 2] c...
Scheme 73: Asymmetric synthesis of thietane-fused β-lactams 356 via the intramolecular photo [2 + 2] cycloaddi...
Scheme 74: Synthesis of the bridged bis(trifluoromethyl)thietane from 2,2,4,4-tetrakis(trifluoromethyl)-1,3-di...
Scheme 75: Synthesis of the bridged-difluorothietane 368 from 2,2,4,4-tetrafluoro-1,3-dithietane (367) and qua...
Scheme 76: Synthesis of bis(trifluoromethyl)thietanes from 2,2,4,4-tetrakis(trifluoromethyl)-1,3-dithietane (3...
Scheme 77: Synthesis of 2,2-dimethylthio-4,4-di(trifluoromethyl)thietane (378) from 2,2,4,4-tetrakis(trifluoro...
Scheme 78: Formation of bis(trifluoromethyl)thioacetone (381) through nucleophilic attack of dithietane 363 by...
Scheme 79: Synthesis of 2,2-bis(trifluoromethyl)thietanes from 2,2,4,4-tetrakis(trifluoromethyl)-1,3-dithietan...
Scheme 80: Synthesis of the bridged bis(trifluoromethyl)thietane 364 from of 2,2,4,4-tetrakis(trifluoromethyl)...
Scheme 81: Synthesis of 2,4-diiminothietanes 390 from alkenimines and 4-methylbenzenesulfonyl isothiocyanate (...
Scheme 82: Synthesis of arylidene 2,4-diiminothietanes 393 starting from phosphonium ylides 391 and isothiocya...
Scheme 83: Synthesis of thietane-2-ylideneacetates 397 through a DABCO-catalyzed formal [2 + 2] cycloaddition ...
Scheme 84: Synthesis of 3-substituted thietanes 400 from (1-chloroalkyl)thiiranes 398.
Scheme 85: Synthesis of N-(thietane-3-yl)azaheterocycles 403 and 404 through reaction of chloromethylthiirane (...
Scheme 86: Synthesis of 3-sulfonamidothietanes 406 from sulfonamides and chloromethylthiirane (398a).
Scheme 87: Synthesis of N-(thietane-3-yl)isatins 408 from chloromethylthiirane (398a) and isatins 407.
Scheme 88: Synthesis of 3-(nitrophenyloxy)thietanes 410 from nitrophenols 409 and chloromethylthiirane (398a).
Scheme 89: Synthesis of N-aryl-N-(thietane-3-yl)cyanamides 412 from N-arylcyanamides 411 and chloromethylthiir...
Scheme 90: Synthesis of 1-(thietane-3-yl)pyrimidin-2,4(1H,3H)-diones 414 from chloromethylthiirane (398a) and ...
Scheme 91: Synthesis of 2,4-diiminothietanes 418 from 2-iminothiiranes 416 and isocyanoalkanes 415.
Scheme 92: Synthesis of 2-vinylthietanes 421 from thiiranes 419 and 3-chloroallyl lithium (420).
Scheme 93: Synthesis of thietanes from thiiranes 419 and trimethyloxosulfonium iodide 424.
Scheme 94: Mechanism for synthesis of thietanes 425 from thiiranes 419 and trimethyloxosulfonium iodide 424.
Scheme 95: Synthesis of functionalized thietanes from thiiranes and dimethylsulfonium acylmethylides.
Scheme 96: Mechanism for the rhodium-catalyzed synthesis of functionalized thietanes 429 from thiiranes 419 an...
Scheme 97: Synthesis of 3-iminothietanes 440 through thermal isomerization from 4,5-dihydro-1,3-oxazole-4-spir...
Scheme 98: Synthesis of thietanes 443 from 3-chloro-2-methylthiolane (441) through ring contraction.
Scheme 99: Synthesis of an optically active thietanose 447 from D-xylose involving a ring contraction.
Scheme 100: Synthesis of optically thietane 447 via the DAST-mediated ring contraction of 448.
Scheme 101: Synthesis of the optically thietane nucleoside 451 via the ring contraction of thiopentose in 450.
Scheme 102: Synthesis of spirothietane 456 from 3,3,5,5-tetramethylthiolane-2,4-dithione (452) and benzyne (453...
Scheme 103: Synthesis of thietanes 461 via photoisomerization of 2H,6H-thiin-3-ones 459.
Scheme 104: Phosphorodithioate-mediated synthesis of 1,4-diarylthietanes 465.
Scheme 105: Mechanism of the phosphorodithioate-mediated synthesis of 1,4-diarylthietanes 465.
Scheme 106: Phosphorodithioate-mediated synthesis of trisubstituted thietanes (±)-470.
Scheme 107: Mechanism on the phosphorodithioate-mediated synthesis of trisubstituted thietanes.
Scheme 108: Phosphorodithioate-mediated synthesis of thietanes (±)-475.
Scheme 109: Phosphorodithioate-mediated synthesis of 1,2-disubstituted thietanes from aldehydes 476 and acrylon...
Scheme 110: Phosphorodithioate-mediated synthesis of 1,2-disubstituted thietanes via a one-pot three-component ...
Scheme 111: Mechanism for the phosphorodithioate-mediated synthesis of 1,2-disubstituted thietanes via three-co...
Scheme 112: Phosphorodithioate-mediated synthesis of substituted 3-nitrothietanes.
Scheme 113: Mechanism on the phosphorodithioate-mediated synthesis of 1,2-disubstituted thietanes (±)-486.
Scheme 114: Asymmetric synthesis of (S)-2-phenylthietane (497).
Scheme 115: Asymmetric synthesis of optically active 2,4-diarylthietanes.
Scheme 116: Synthesis of 3-acetamidothietan-2-one 503 via the intramolecular thioesterification of 3-mercaptoal...
Scheme 117: Synthesis of 4-substituted thietan-2-one via the intramolecular thioesterification of 3-mercaptoalk...
Scheme 118: Synthesis of 4,4-disubstituted thietan-2-one 511 via the intramolecular thioesterification of the 3...
Scheme 119: Synthesis of a spirothietan-2-one 514 via the intramolecular thioesterification of 3-mercaptoalkano...
Scheme 120: Synthesis of thiatetrahydrolipstatin starting from (S)-(−)-epichlorohydrin ((S)-142a).
Scheme 121: Synthesis of 2-phenethyl-4-(propan-2-ylidene)thietane (520) from 5-bromo-6-methyl-1-phenylhept-5-en...
Scheme 122: Synthesis of 2-phenethyl-4-(propan-2-ylidene)thietane (520) directly from S-(5-bromo-6-methyl-1-phe...
Scheme 123: Synthesis of 2-alkylidenethietanes from S-(2-bromoalk-1-en-4-yl)thioacetates.
Scheme 124: Synthesis of 2-alkylidenethietanes from S-(2-bromo/chloroalk-1-en-4-yl)thiols.
Scheme 125: Synthesis of spirothietan-3-ol 548 from enone 545 and ammonium hydrosulfide.
Scheme 126: Asymmetric synthesis of the optically active thietanoside from cis-but-2-ene-1,4-diol (47).
Scheme 127: Synthesis of 2-alkylidenethietan-3-ols 557 via the fluoride-mediated cyclization of thioacylsilanes ...
Scheme 128: Synthesis of 2-iminothietanes via the reaction of propargylbenzene (558) and isothiocyanates 560 in...
Scheme 129: Synthesis of 2-benzylidenethietane 567 via the nickel complex-catalyzed electroreductive cyclizatio...
Scheme 130: Synthesis of 2-iminothietanes 569 via the photo-assisted electrocyclic reaction of N-monosubstitute...
Scheme 131: Synthesis of ethyl 3,4-diiminothietane-2-carboxylates from ethyl thioglycolate (570) and bis(imidoy...
Scheme 132: Synthesis of N-(thietan-3-yl)-α-oxoazaheterocycles from azaheterocyclethiones and chloromethyloxira...
Scheme 133: Synthesis of thietan-3-yl benzoate (590) via the nickel-catalyzed intramolecular reductive thiolati...
Scheme 134: Synthesis of 2,2-bis(trifluoromethyl)thietane from 3,3-bis(trifluoromethyl)-1,2-dithiolane.
Scheme 135: Synthesis of thietanes from enamines and sulfonyl chlorides.
Scheme 136: Synthesis of spirothietane 603 via the [2 + 3] cycloaddition of 2,2,4,4-tetramethylcyclobutane-1,3-...
Scheme 137: Synthesis of thietane (605) from 1-bromo-3-chloropropane and sulfur.
Beilstein J. Org. Chem. 2020, 16, 1288–1295, doi:10.3762/bjoc.16.109
Graphical Abstract
Scheme 1: Synthesis of spirotetrahydrothiophenes 3 via non-concerted [3 + 2]-cycloadditions of thiocarbonyl y...
Scheme 2: Formal [3 + 2]-cycloadditions of thioketones and [4 + 3]-cycloadditions of thiochalcones with donor...
Scheme 3: Formal [3 + 2]-cycloadditions of dimethyl 2-substituted cyclopropane-1,1-dicarboxylates 5a–g with f...
Figure 1: Thermal ellipsoid plots of the molecular structures of cis-9c and trans-9d drawn using 50% probabil...
Scheme 4: Plausible mechanism for the formal [3 + 2]-cycloadditions of ferrocenyl thioketones 8 with D–A cycl...
Beilstein J. Org. Chem. 2019, 15, 2311–2318, doi:10.3762/bjoc.15.223
Graphical Abstract
Figure 1: General structure of aryl-λ3-iodanes.
Figure 2: Tpeak and ΔHdec-values for a range of N- and O-substituted iodanes.
Figure 3: TGA/DSC curves of (a) benziodoxolone 1, (b) triazole 2 and (c) pyrazole 6.
Figure 4: Decomposition enthalpy (ΔHdec) scale for pseudocyclic tosylates 1–15 and cyclic iodoso species 16 a...
Figure 5: Correlation between the relative reactivity for pseudocyclic NHIs based on the reaction time in the...
Figure 6: Tpeak and ΔHdec values for a range of N- and O-substituted iodanes.
Figure 7: Decomposition enthalpy (ΔHdec) scale for (pseudo)cyclic mesitylen(phenyl)- λ3-iodanes 18–33.
Figure 8: TGA/DSC curves for the benzimidazole based diaryliodonium salt 25.
Figure 9: TGA/DSC curves for the cyclic triazole 32.
Scheme 1: The thermal decomposition of (pseudo)cyclic N-heterocycle-stabilized mesityl(aryl)-λ3-iodanes 25 an...
Beilstein J. Org. Chem. 2018, 14, 1317–1348, doi:10.3762/bjoc.14.113
Graphical Abstract
Scheme 1: Thermal reaction of sydnones with symmetrical alkynes.
Scheme 2: Reaction of sydnones with strained cycloalkynes.
Scheme 3: Reaction of sydnones with didehydrobenzenes.
Scheme 4: Formation of isomeric pyrazole dicarboxylates.
Scheme 5: Mechanism of thermal cycloaddition between sydnones and alkynes.
Scheme 6: Mechanism of photochemical reaction of sydnones with symmetrical alkynes.
Scheme 7: HOMO–LUMO diagram for thermal [3 + 2]-cycloaddition of sydnones with alkynes.
Scheme 8: Synthetic strategy leading to 1,2-disubstituted pyrazoles.
Scheme 9: Unsuccessful reaction with phenylpropiolic acid.
Scheme 10: Synthetic strategy leading to 1,4,5-trisubstituted pyrazoles.
Scheme 11: Reaction of sydnones carrying in position 4- six-membered 2-N-heterocyclic ring.
Scheme 12: Strain-promoted sydnone alkyne cycloaddition (SPSAC).
Scheme 13: Synthesis of a key intermediate of niraparib.
Scheme 14: Reaction of sydnones with 1,3-/1,4-benzdiyne equivalents.
Scheme 15: Reaction of sydnones with heterocyclic strained cycloalkynes.
Scheme 16: Mono-copper catalyzed cycloaddition reaction.
Scheme 17: Di-copper catalyzed cycloaddition reaction.
Beilstein J. Org. Chem. 2018, 14, 1287–1292, doi:10.3762/bjoc.14.110
Graphical Abstract
Scheme 1: Envisaged approach for the synthesis of 5-chloropyrazole-4-carboxylates 2.
Scheme 2: Synthesis of bipyrazolone 3a.
Figure 1: Signal of the OCH2 ester protons of reaction product 3a (500 MHz, CDCl3).
Figure 2: ORTEP-plot of the crystal structure of compound 3a drawn with 50% displacement ellipsoids [(4S,4'S)-...
Figure 3: Arrangement (4R,4'R)- and (4S,4'S)-3a enantiomers in the crystal unit drawn with 50% displacement e...
Scheme 3: Synthesis of compounds 3a–i.
Scheme 4: Reaction of different 5-hydroxypyrazoles with thionyl chloride.
Scheme 5: Reaction of 1a with sulfuryl chloride.
Scheme 6: Possible reaction mechanism for the transformation 1 → 3.
Scheme 7: Preparation of bipyrazoles 10.
Figure 4: 1H NMR (italics), 13C NMR (normal letters) and 15N NMR (in bold) chemical shifts of 3a (in CDCl3).
Beilstein J. Org. Chem. 2017, 13, 2235–2251, doi:10.3762/bjoc.13.221
Graphical Abstract
Figure 1: Dialkyl dicyanofumarates E-1 and dicyanomaleates Z-1.
Scheme 1: Methods for the synthesis of dialkyl dicyanofumarates E-1 from alkyl cyanoacetates 2.
Scheme 2: Methods for the synthesis of dialkyl dicyanofumarates E-1 from alkyl bromoacetates 3.
Scheme 3: Reaction of dimethyl dicyanofumarate (E-1b) with dimethoxycarbene [(MeO)2C:] generated in situ from...
Scheme 4: Cyclopropanation of diethyl dicyanofumarate (E-1a) through reaction with the thiophene derived sulf...
Scheme 5: Cyclopropanation of dimethyl dicyanofumarate (E-1b) through a stepwise reaction with the in situ ge...
Scheme 6: The [2 + 2]-cycloadditions of dimethyl dicyanofumarate (E-1b) with electron-rich ethylenes 20 and 22...
Scheme 7: The [2 + 2]-cycloaddition of isomeric dimethyl dicyanofumarate (E-1b) and dicyanomaleate (Z-1b) wit...
Scheme 8: Non-concerted [2 + 2]-cycloaddition between E-1b and bicyclo[2.1.0]pentene (27).
Scheme 9: Stepwise [3 + 2]-cycloadditions of some thiocarbonyl S-methanides with dialkyl dicyanofumarates E-1...
Scheme 10: Stepwise [3 + 2]-cycloadditions of dimethyl dicyanofumarate (E-1b) and dimethyl dicyanomaleate (Z-1b...
Scheme 11: [3 + 2]-Cycloaddition of diazomethane with dimethyl dicyanofumarate (E-1b) leading to 1H-pyrazole d...
Scheme 12: Reversible Diels–Alder reaction of fulvenes 36 with diethyl dicyanofumarate (E-1a).
Scheme 13: [4 + 2]-Cycloaddition of 9,10-dimethylanthracene (39b) and E-1a.
Scheme 14: Stepwise [4 + 2]-cycloaddition of dimethyl dicyanofumarate (E-1b) with electron-rich 1,1-dimethoxy-...
Scheme 15: Formal [4 + 2]-cycloaddition of 3,4-di(α-styryl)furan (47) with dimethyl dicyanofumarate (E-1b).
Scheme 16: Acid-catalyzed Michael addition of enolizable ketones of type 49 to E-1.
Scheme 17: Reaction of diethyl dicyanofumarate (E-1a) with ammonia NH3.
Scheme 18: Reaction of dialkyl dicyanofumarates E-1 with primary and secondary amines.
Scheme 19: Reaction of dialkyl dicyanofumarates E-1 with 1-azabicyclo[1.1.0]butanes 55.
Scheme 20: Formation of pyrazole derivatives in the reaction of hydrazines with E-1.
Scheme 21: Formation of 5-aminopyrazole-3,4-dicarboxylate 65 via heterocyclization reactions.
Scheme 22: Reactions of aryl- and hetarylcarbohydrazides 67 with E-1a.
Scheme 23: Multistep reaction leading to perhydroquinoxaline derivative 73.
Scheme 24: Synthesis of ethyl 7-aminopteridin-6-carboxylates 75 via a domino reaction.
Scheme 25: Synthesis of morhpolin-2-ones 80 from E-1 and β-aminoalcohols 78 through an initial aza-Michael add...
Scheme 26: Reaction of 3-amino-5-arylpyrazoles 81 with dialkyl dicyanofumarates E-1 via competitive nucleophil...
Scheme 27: Heterocyclization reaction of thiosemicarbazone 86 with E-1a.
Scheme 28: Formation of diethyl 4-cyano-5-oxotetrahydro-4H-chromene-3,4-dicarboxylate (90) from E-1a via heter...
Scheme 29: Reaction of dialkyl dicyanofumarates E-1 with cysteamine (92).
Scheme 30: Formation of disulfides through reaction of thiols with E-1a.
Scheme 31: Formation of CT salts of E-1 with Mn2+ and Cr2+ metallocenes through one-electron transfer.
Scheme 32: Oxidation of diethyl dicyanofumarate (E-1a) with H2O2 to give oxirane 101.
Scheme 33: The aziridination of E-1b through nitrene addition.
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, 260–270, doi:10.3762/bjoc.12.28
Graphical Abstract
Scheme 1: Lewis acid-catalyzed [1,4]-H transfer/1,5-electrocyclization tandem processes of benzylidenemalonat...
Scheme 2: Preparation of benz[f]indenes 5 and 6. Reagents and conditions: i) cyclopentadiene, pyrrolidine, an...
Scheme 3: Postulated reaction path for the conversion 3a → 5a + 6a initiated by a [1,4]-hydride shift.
Scheme 4: Alternative mechanistic paths for the conversion 3a → 5a + 6a initiated by [1,5]-, [1,7]- or [1,9]-...
Scheme 5: Postulated outcome of the conversion 14 → 18 + 19 initiated by a [1,4]-deuteride shift.
Scheme 6: Preparation of deuterated benz[f]indenes 18 + 19 and 21 + 22. Reagents and conditions: i) DMSO, mic...
Scheme 7: Reagents and conditions: i) triethylamine (10%), DMSO, rt, 2 h.
Scheme 8: Preparation of benz[f]indenes 25 and 26. Reagents and conditions: i) cyclopentadiene, pyrrolidine, ...
Scheme 9: Mechanistic paths for the conversion of fulvene 3a into the benz[f]indenes 5a and 6a showing the en...
Figure 1: Optimized geometry of transition structures TS1-A, TS1-B, and TS1-C computed at the B3LYP/6-31+G** ...
Beilstein J. Org. Chem. 2016, 12, 239–244, doi:10.3762/bjoc.12.25
Graphical Abstract
Scheme 1: Palladium-catalyzed ring-opening reactions of oxabenzonorbornadiene.
Scheme 2: Palladium-catalyzed ring-opening of 1 with p-iodotoluene.
Scheme 3: Potential regioisomers from the palladium-catalyzed ring-opening reaction of 2 with aryl iodides.
Scheme 4: Palladium-catalyzed ring-opening of C1 substituted oxabenzonorbornadiene.
Scheme 5: Proposed mechanism for the palladium-catalyzed ring-opening reaction of oxanorbornadiene.
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, 1583–1595, doi:10.3762/bjoc.11.174
Graphical Abstract
Scheme 1: Activated derivatives of dicarboxylic acids.
Figure 1: Example of natural compounds selectively acylated with dicarboxylic esters.
Figure 2: C6-dicarboxylic acid diesters derivatives of NAG-thiazoline.
Figure 3: Sylibin dimers obtained by CAL-B catalyzed trans-acylation reactions.
Scheme 2: Biocatalyzed synthesis of paclitaxel derivatives.
Figure 4: 5-Fluorouridine derivatives obtained by CAL-B catalysis.
Scheme 3: Biocatalyzed synthesis of hybrid diesters 17 and 18.
Scheme 4: Hybrid derivatives of sylibin.
Figure 5: Bolaamphiphilic molecules containing (L)- and/or (D)-isoascorbic acid moieties.
Figure 6: Doxorubicin (29) trapped in a polyester made of glycolate, sebacate and 1,4-butandiol units.
Figure 7: Polyesters containing functionalized pentofuranose derivatives.
Figure 8: Polyesters containing disulfide moieties.
Figure 9: Polyesters containing epoxy moieties.
Figure 10: Biocatalyzed synthesis of polyesters containing glycerol.
Figure 11: Iataconic (34) and malic (35) acid.
Figure 12: Oxidized poly(hexanediol-2-mercaptosuccinate) polymer.
Figure 13: C-5-substituted isophthalates.
Figure 14: Curcumin-based polyesters.
Figure 15: Silylated polyesters.
Figure 16: Polyesters containing reactive ether moieties.
Figure 17: Polyesters obtained by CAL-B-catalyzed condensation of dicarboxylic esters and N-substituted dietha...
Figure 18: Polyesters comprising mexiletine (38) moieties.
Figure 19: Poly(amide-co-ester)s comprising a terminal hydroxy moiety.
Figure 20: Polymer comprising α-oxydiacid moieties.
Figure 21: Telechelics with methacrylate ends.
Figure 22: Telechelics with allyl-ether ends.
Figure 23: Telechelics with ends functionalized as epoxides.
Beilstein J. Org. Chem. 2015, 11, 1340–1351, doi:10.3762/bjoc.11.144
Graphical Abstract
Scheme 1: Reaction of carbon dioxide with epoxide to yield alternating polycarbonates, polyethercarbonates or...
Scheme 2: Epoxide and CO2 copolymerisation by homogeneous Cr(III)– and Al(III)–salen complexes.
Figure 1: The tri-coordinated di-iminate zinc–alkoxide complex [(BDI)ZnOCH3].
Scheme 3: Heterogeneous zinc dicarboxylates for the copolymerisation of CO2 and epoxides. (* = End group of p...
Scheme 4: Backbiting mechanism for the formation of cyclic carbonates.
Scheme 5: Two-step pathway for the cycloaddition of propylene oxide and CO2 in the ionic liquid 1-butyl-3-met...
Scheme 6: Formation of copper(I) cyanoacetate for the activation of CO2.
Scheme 7: Activation of CO2 by nucleophilic attack of bromide in the Re(I)-catalysed cycloaddition.
Scheme 8: Direct catalytic carboxylation of aliphatic compounds and arenes by rhodium(I)– and ruthenium(II)–p...
Scheme 9: Insertion of carbon dioxide into a metal–oxygen bond via a cyclic four-membered transition state. R...
Scheme 10: Facile CO2 uptake by zinc(II)–tetraazacycloalkanes.
Figure 2: The [(2-hydroxyethoxy)CoIII(salen)(L)] complex chosen as catalyst model for the calculations; 1: R1...
Figure 3: The two most relevant configurations of [(2-hydroxyethoxy)CoIII(salen)(L)] complexes. The left-hand...
Figure 4: Carbon dioxide insertion into the cobalt(III)–alkoxide bond of [(2-hydroxyethoxy)CoIII(salen)(L)] c...
Figure 5: Energy relationship between the activation barrier and the reaction energy of the CO2 incorporation...
Beilstein J. Org. Chem. 2015, 11, 576–582, doi:10.3762/bjoc.11.63
Graphical Abstract
Scheme 1: Hetero-Diels–Alder reaction of thiobenzophenone (1a) with dimethyl acetylenedicarboxylate (2a) [10].
Scheme 2: Synthesis of polycyclic thiopyrans via the hetero-Diels–Alder reaction/1,3-hydrogen shift sequence.
Figure 1: ORTEP Plot [19] of the molecular structure of 4b, drawn using 50% probability displacement ellipsoids.
Scheme 3: Reactions of aryl/hetaryl thioketones with methyl propiolate (Table 1).
Scheme 4: Oxidation of selected thiopyrans 4 and 5 to give the corresponding sulfones.
Figure 2: ORTEP Plot [19] of the molecular structure of one of the symmetry-independent molecules of 6d, drawn us...