Search for "sodium sulfinates" in Full Text gives 13 result(s) in Beilstein Journal of Organic Chemistry.
Beilstein J. Org. Chem. 2025, 21, 253–261, doi:10.3762/bjoc.21.17
Graphical Abstract
Scheme 1: Different strategies for the synthesis of disulfides and 3-sulfenylchromones.
Scheme 2: Substrate scope for the synthesis of disulfides. Reaction conditions: 1 (1 mmol), TBAI (0.2 mmol), H...
Scheme 3: Substrate scope for the synthesis of 3-sulfenylchromones. Reaction conditions: 1 (1 mmol), 3 (0.5 m...
Scheme 4: Gram-scale synthesis of 2a and 4a and one-pot synthesis of 4a.
Scheme 5: Control experiments.
Scheme 6: Plausible reaction mechanism.
Beilstein J. Org. Chem. 2024, 20, 2883–2890, doi:10.3762/bjoc.20.242
Graphical Abstract
Scheme 1: State of the art and this work.
Scheme 2: Reaction conditions: hydrazone (0.3 mmol, 1.0 equiv), NBS (0.33 mmol, 1.1 equiv), in CH3CN (0.4 M),...
Scheme 3: Scope of the reaction. Reaction conditions: 1 (0.3 mmol, 1.0 equiv), NBS (0.33 mmol, 1.1 equiv) in ...
Scheme 4: Mechanistic investigations and post-functionalization reactions. a19F NMR yields using α,α,α-triflu...
Beilstein J. Org. Chem. 2024, 20, 2739–2775, doi:10.3762/bjoc.20.232
Graphical Abstract
Scheme 1: Copper-catalyzed allylic and yne-allylic substitution.
Scheme 2: Challenges in achieving highly selective yne-allylic substitution.
Scheme 3: Yne-allylic substitutions using indoles and pyroles.
Scheme 4: Yne-allylic substitutions using amines.
Scheme 5: Yne-allylic substitution using 1,3-dicarbonyls.
Scheme 6: Postulated mechanism via copper acetylide-bonded allylic cation.
Scheme 7: Amine-participated asymmetric yne-allylic substitution.
Scheme 8: Asymmetric decarboxylative yne-allylic substitution.
Scheme 9: Asymmetric yne-allylic alkoxylation and alkylation.
Scheme 10: Proposed mechanism for Cu(I) system.
Scheme 11: Asymmetric yne-allylic dialkylamination.
Scheme 12: Proposed mechanism of yne-allylic dialkylamination.
Scheme 13: Asymmetric yne-allylic sulfonylation.
Scheme 14: Proposed mechanism of yne-allylic sulfonylation.
Scheme 15: Aymmetric yne-allylic substitutions using indoles and indolizines.
Scheme 16: Double yne-allylic substitutions using pyrrole.
Scheme 17: Proposed mechanism of yne-allylic substitution using electron-rich arenes.
Scheme 18: Aymmetric yne-allylic monofluoroalkylations.
Scheme 19: Proposed mechanism.
Scheme 20: Aymmetric yne-allylic substitution of yne-allylic esters with anthrones.
Scheme 21: Aymmetric yne-allylic substitution of yne-allylic esters with coumarins.
Scheme 22: Aymmetric yne-allylic substitution of with coumarins by Lin.
Scheme 23: Proposed mechanism.
Scheme 24: Amination by alkynylcopper driven dearomatization and rearomatization.
Scheme 25: Arylation by alkynylcopper driven dearomatization and rearomatization.
Scheme 26: Remote substitution/cyclization/1,5-H shift process.
Scheme 27: Proposed mechanism.
Scheme 28: Arylation or amination by alkynylcopper driven dearomatization and rearomatization.
Scheme 29: Remote nucleophilic substitution of 5-ethynylthiophene esters.
Scheme 30: Proposed mechanism.
Scheme 31: [4 + 1] annulation of yne-allylic esters and cyclic 1,3-dicarbonyls.
Scheme 32: Asymmetric [4 + 1] annulation of yne-allylic esters.
Scheme 33: Proposed mechanism.
Scheme 34: Asymmetric [3 + 2] annulation of yne-allylic esters.
Scheme 35: Postulated annulation step.
Scheme 36: [4 + 1] Annulations of vinyl ethynylethylene carbonates and 1,3-dicarbonyls.
Scheme 37: Proposed mechanism.
Scheme 38: Formal [4 + 1] annulations with amines.
Scheme 39: Formal [4 + 2] annulations with hydrazines.
Scheme 40: Proposed mechanism.
Scheme 41: Dearomative annulation of 1-naphthols and yne-allylic esters.
Scheme 42: Dearomative annulation of phenols or 2-naphthols and yne-allylic esters.
Scheme 43: Postulated annulation mechanism.
Scheme 44: Dearomative annulation of phenols or 2-naphthols.
Scheme 45: Dearomative annulation of indoles.
Scheme 46: Postulated annulation step.
Scheme 47: Asymmetric [4 + 1] cyclization of yne-allylic esters with pyrazolones.
Scheme 48: Proposed mechanism.
Scheme 49: Construction of C–C axially chiral arylpyrroles.
Scheme 50: Construction of C–N axially chiral arylpyrroles.
Scheme 51: Construction of chiral arylpyrroles with 1,2-di-axial chirality.
Scheme 52: Proposed mechanism.
Scheme 53: CO2 shuttling in yne-allylic substitution.
Scheme 54: CO2 fixing in yne-allylic substitution.
Scheme 55: Proposed mechanism.
Beilstein J. Org. Chem. 2024, 20, 1988–2004, doi:10.3762/bjoc.20.175
Graphical Abstract
Scheme 1: Synthesis of triazolopyridinium salts [34-36].
Scheme 2: Synthesis of pyrazoles [37].
Scheme 3: Synthesis of indazoles from ketone-derived hydrazones [38].
Scheme 4: Intramolecular C(sp2)–H functionalization of aldehyde-derived N-(2-pyridinyl)hydrazones for the syn...
Scheme 5: Synthesis of pyrazolo[4,3-c]quinoline derivatives [40].
Scheme 6: Synthesis of 1,3,4-oxadiazoles and Δ3-1,3,4-oxadiazolines [41].
Scheme 7: Synthesis of 1,3,4-oxadiazoles [43].
Scheme 8: Synthesis of 2-(1,3,4-oxadiazol-2-yl)anilines [44].
Scheme 9: Synthesis of fused s-triazolo perchlorates [45].
Scheme 10: Synthesis of 1-aryl and 1,5-disubstitued 1,2,4-triazoles [49].
Scheme 11: Synthesis of 1,3,5-trisubstituted 1,2,4-triazoles [50].
Scheme 12: Alternative synthesis of 1,3,5-trisubstituted 1,2,4-triazoles [51].
Scheme 13: Synthesis of 5-amino 1,2,4-triazoles [55].
Scheme 14: Synthesis of 1-arylpyrazolines [58].
Scheme 15: Synthesis of 3‑aminopyrazoles [60].
Scheme 16: Synthesis of [1,2,4]triazolo[4,3-a]quinolines [61].·
Scheme 17: Synthesis of 1,2,3-thiadiazoles [64].
Scheme 18: Synthesis of 5-thioxo-1,2,4-triazolium inner salts [65].
Scheme 19: Synthesis of 1-aminotetrazoles [66].
Scheme 20: C(sp2)–H functionalization of aldehyde-derived hydrazones: general mechanisms.
Scheme 21: C(sp2)–H functionalization of benzaldehyde diphenyl hydrazone [68,69].
Scheme 22: Phosphorylation of aldehyde-derived hydrazones [70].
Scheme 23: Azolation of aldehyde-derived hydrazones [72].
Scheme 24: Thiocyanation of benzaldehyde-derived hydrazone 122 [73].
Scheme 25: Sulfonylation of aromatic aldehyde-derived hydrazones [74].
Scheme 26: Trifluoromethylation of aromatic aldehyde-derived hydrazones [76].
Scheme 27: Electrooxidation of benzophenone hydrazones [77].
Scheme 28: Electrooxidative coupling of benzophenone hydrazones and alkenes [77].
Scheme 29: Electrosynthesis of α-diazoketones [78].
Scheme 30: Electrosynthesis of stable diazo compounds [80].
Scheme 31: Photoelectrochemical synthesis of alkenes through in situ generation of diazo compounds [81].
Scheme 32: Synthesis of nitriles [82].
Scheme 33: Electrochemical oxidation of ketone-derived NH-allylhydrazone [83].
Beilstein J. Org. Chem. 2024, 20, 675–683, doi:10.3762/bjoc.20.61
Graphical Abstract
Scheme 1: Approaches for quinazoline modifications at the C2 and C4 positions.
Scheme 2: Attempts toward sulfonyl group dance using 2,4-dichloroquinazolines 1a‒c.
Scheme 3: Synthesis of 2-chloro-6,7-dimethoxy-4-sulfonylquinazoline derivatives 8.
Scheme 4: Alternative synthesis pathway for 2-chloro-6,7-dimethoxy-4-sulfonylquinazoline derivatives 8.
Scheme 5: Sulfonyl group dance using 2-chloro-6,7-dimethoxy-4-sulfonylquinazolines 8.
Scheme 6: One-pot synthesis of 4-azido-6,7-dimethoxy-2-sulfonylquinazolines 12. The crystallographic informat...
Scheme 7: Synthesis of 2-azido-4-sulfonyl-6,7-dimethoxyquinazolines 15.
Scheme 8: Synthesis of 6,7-dimethoxyquinazoline derivatives 16, 17a and 18.
Scheme 9: Synthesis of 2-amino-4-azido-6,7-dimethoxyquinazolines 17.
Scheme 10: Synthesis of terazosin and prazosin hydrochlorides 19a and 19b.
Scheme 11: Modifications of derivatives 17.
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. 2022, 18, 1123–1130, doi:10.3762/bjoc.18.115
Graphical Abstract
Figure 1: Different approaches to heterogeneous photochemistry in flow. a) Serial micro-batch reactors (SMBR)...
Figure 2: Light-mediated carbon–heteroatom cross-couplings. The yields reported are the NMR yields obtained i...
Figure 3: Flow diagram of the experimental setup loaded in an injection loop with the reaction mixture.
Figure 4: Flow diagram of the experimental setup adopted and time necessary to obtain steady-state conditions...
Figure 5: The production campaign of 1 for a seven day experiment.
Figure 6: Photo of the packed column with a helical static mixer (polished SS316, 10 cm length, 15 mixing ele...
Scheme 1: C–O coupling between 4-iodobenzotrifluoride and N-(Boc)-proline.
Beilstein J. Org. Chem. 2020, 16, 1754–1804, doi:10.3762/bjoc.16.147
Graphical Abstract
Figure 1: Concept of dual synergistic catalysis.
Figure 2: Classification of catalytic systems involving two catalysts.
Figure 3: General mechanism for the dual nickel/photoredox catalytic system.
Figure 4: General mechanisms for C–H activation catalysis involving different reoxidation strategies.
Figure 5: Indole synthesis via dual C–H activation/photoredox catalysis.
Figure 6: Proposed mechanism for the indole synthesis via dual catalysis.
Figure 7: Oxidative Heck reaction on arenes via the dual catalysis.
Figure 8: Proposed mechanism for the Heck reaction on arenes via dual catalysis.
Figure 9: Oxidative Heck reaction on phenols via the dual catalysis.
Figure 10: Proposed mechanism for the Heck reaction on phenols via dual catalysis.
Figure 11: Carbazole synthesis via dual C–H activation/photoredox catalysis.
Figure 12: Proposed mechanism for the carbazole synthesis via dual catalysis.
Figure 13: Carbonylation of enamides via the dual C–H activation/photoredox catalysis.
Figure 14: Proposed mechanism for carbonylation of enamides via dual catalysis.
Figure 15: Annulation of benzamides via the dual C–H activation/photoredox catalysis.
Figure 16: Proposed mechanism for the annulation of benzamides via dual catalysis.
Figure 17: Synthesis of indoles via the dual C–H activation/photoredox catalysis.
Figure 18: Proposed mechanism for the indole synthesis via dual catalysis.
Figure 19: General concept of dual catalysis merging C–H activation and photoredox catalysis.
Figure 20: The first example of dual catalysis merging C–H activation and photoredox catalysis.
Figure 21: Proposed mechanism for the C–H arylation with diazonium salts via dual catalysis.
Figure 22: Dual catalysis merging C–H activation/photoredox using diaryliodonium salts.
Figure 23: Direct arylation via the dual catalytic system reported by Xu.
Figure 24: Direct arylation via dual catalytic system reported by Balaraman.
Figure 25: Direct arylation via dual catalytic system reported by Guo.
Figure 26: C(sp3)–H bond arylation via the dual Pd/photoredox catalytic system.
Figure 27: Acetanilide derivatives acylation via the dual C–H activation/photoredox catalysis.
Figure 28: Proposed mechanism for the C–H acylation with α-ketoacids via dual catalysis.
Figure 29: Acylation of azobenzenes via the dual catalysis C–H activation/photoredox.
Figure 30: C2-acylation of indoles via the dual C–H activation/photoredox catalysis.
Figure 31: Proposed mechanism for the C2-acylation of indoles with aldehydes via dual catalysis.
Figure 32: C2-acylation of indoles via the dual C–H activation/photoredox catalysis.
Figure 33: Perfluoroalkylation of arenes via the dual C–H activation/photoredox catalysis.
Figure 34: Proposed mechanism for perfluoroalkylation of arenes via dual catalysis.
Figure 35: Sulfonylation of 1-naphthylamides via the dual C–H activation/photoredox catalysis.
Figure 36: Proposed mechanism for sulfonylation of 1-naphthylamides via dual catalysis.
Figure 37: meta-C–H Alkylation of arenes via visible-light metallaphotocatalysis.
Figure 38: Alternative procedure for meta-C–H alkylation of arenes via metallaphotocatalysis.
Figure 39: Proposed mechanism for meta-C–H alkylation of arenes via metallaphotocatalysis.
Figure 40: C–H borylation of arenes via visible-light metallaphotocatalysis.
Figure 41: Proposed mechanism for C–H borylation of arenes via visible-light metallaphotocatalysis.
Figure 42: Undirected C–H aryl–aryl cross coupling via dual gold/photoredox catalysis.
Figure 43: Proposed mechanism for the undirected C–H aryl–aryl cross-coupling via dual catalysis.
Figure 44: Undirected C–H arylation of (hetero)arenes via dual manganese/photoredox catalysis.
Figure 45: Proposed mechanism for the undirected arylation of (hetero)arenes via dual catalysis.
Figure 46: Photoinduced C–H arylation of azoles via copper catalysis.
Figure 47: Photo-induced C–H chalcogenation of azoles via copper catalysis.
Figure 48: Decarboxylative C–H adamantylation of azoles via dual cobalt/photoredox catalysis.
Figure 49: Proposed mechanism for the C–H adamantylation of azoles via dual catalysis.
Figure 50: General mechanisms for the “classical” (left) and Cu-free variant (right) Sonogoshira reaction.
Figure 51: First example of a dual palladium/photoredox catalysis for Sonogashira-type couplings.
Figure 52: Arylation of terminal alkynes with diazonium salts via dual gold/photoredox catalysis.
Figure 53: Proposed mechanism for the arylation of terminal alkynes via dual catalysis.
Figure 54: C–H Alkylation of alcohols promoted by H-atom transfer (HAT).
Figure 55: Proposed mechanism for the C–H alkylation of alcohols promoted by HAT.
Figure 56: C(sp3)–H arylation of latent nucleophiles promoted by H-atom transfer.
Figure 57: Proposed mechanism for the C(sp3)–H arylation of latent nucleophiles promoted by HAT.
Figure 58: Direct α-arylation of alcohols promoted by H-atom transfer.
Figure 59: Proposed mechanism for the direct α-arylation of alcohols promoted by HAT.
Figure 60: C–H arylation of amines via dual Ni/photoredox catalysis.
Figure 61: Proposed mechanism for the C–H arylation of amines via dual Ni/photoredox catalysis.
Figure 62: C–H functionalization of nucleophiles via excited ketone/nickel dual catalysis.
Figure 63: Proposed mechanism for the C–H functionalization enabled by excited ketones.
Figure 64: Selective sp3–sp3 cross-coupling promoted by H-atom transfer.
Figure 65: Proposed mechanism for the selective sp3–sp3 cross-coupling promoted by HAT.
Figure 66: Direct C(sp3)–H acylation of amines via dual Ni/photoredox catalysis.
Figure 67: Proposed mechanism for the C–H acylation of amines via dual Ni/photoredox catalysis.
Figure 68: C–H hydroalkylation of internal alkynes via dual Ni/photoredox catalysis.
Figure 69: Proposed mechanism for the C–H hydroalkylation of internal alkynes.
Figure 70: Alternative procedure for the C–H hydroalkylation of ynones, ynoates, and ynamides.
Figure 71: Allylic C(sp3)–H activation via dual Ni/photoredox catalysis.
Figure 72: Proposed mechanism for the allylic C(sp3)–H activation via dual Ni/photoredox catalysis.
Figure 73: Asymmetric allylation of aldehydes via dual Cr/photoredox catalysis.
Figure 74: Proposed mechanism for the asymmetric allylation of aldehydes via dual catalysis.
Figure 75: Aldehyde C–H functionalization promoted by H-atom transfer.
Figure 76: Proposed mechanism for the C–H functionalization of aldehydes promoted by HAT.
Figure 77: Direct C–H arylation of strong aliphatic bonds promoted by HAT.
Figure 78: Proposed mechanism for the C–H arylation of strong aliphatic bonds promoted by HAT.
Figure 79: Direct C–H trifluoromethylation of strong aliphatic bonds promoted by HAT.
Figure 80: Proposed mechanism for the C–H trifluoromethylation of strong aliphatic bonds.
Beilstein J. Org. Chem. 2020, 16, 1476–1488, doi:10.3762/bjoc.16.123
Graphical Abstract
Figure 1: Bioactive phenanthridine and phenanthridinium derivatives.
Scheme 1: Synthesis of phenanthrenes by a photo-Pschorr reaction.
Scheme 2: Synthesis of phenanthrenes by a benzannulation reaction.
Scheme 3: Photocatalytic cyclization of α-bromochalcones for the synthesis of phenanthrenes.
Figure 2: Carbon-centered and nitrogen-centered radicals used for the synthesis of phenanthridines.
Scheme 4: General scheme describing the synthesis of phenanthridines from isocyanides via imidoyl radicals.
Scheme 5: Synthesis of substituted phenanthridines involving the intermediacy of electrophilic radicals.
Scheme 6: Photocatalyzed synthesis of 6-β-ketoalkyl phenanthridines.
Scheme 7: Synthesis of 6-substituted phenanthridines through the addition of trifluoromethyl (path a), phenyl...
Scheme 8: Synthesis of 6-(trifluoromethyl)-7,8-dihydrobenzo[k]phenanthridine.
Scheme 9: Phenanthridine syntheses by using photogenerated radicals formed through a C–H bond homolytic cleav...
Scheme 10: Trifluoroacetimidoyl chlorides as starting substrates for the synthesis of 6-(trifluoromethyl)phena...
Scheme 11: Synthesis of phenanthridines via aryl–aryl-bond formation.
Scheme 12: Oxidative conversion of N-biarylglycine esters to phenanthridine-6-carboxylates.
Scheme 13: Photocatalytic synthesis of benzo[f]quinolines from 2-heteroaryl-substituted anilines and heteroary...
Scheme 14: Synthesis of noravicine (14.2a) and nornitidine (14.2b) alkaloids.
Scheme 15: Gram-scale synthesis of the alkaloid trisphaeridine (15.3).
Scheme 16: Synthesis of phenanthridines starting from vinyl azides.
Scheme 17: Synthesis of pyrido[4,3,2-gh]phenanthridines 17.5a–d through the radical trifluoromethylthiolation ...
Scheme 18: The direct oxidative C–H amidation involving amidyl radicals for the synthesis of phenanthridones.
Beilstein J. Org. Chem. 2020, 16, 1234–1276, doi:10.3762/bjoc.16.107
Graphical Abstract
Figure 1: Imine-N-oxyl radicals (IV) discussed in the present review and other classes of N-oxyl radicals (I–...
Figure 2: The products of decomposition of iminoxyl radicals generated from oximes by oxidation with Ag2O.
Scheme 1: Generation of oxime radicals and study of the kinetics of their decay by photolysis of the solution...
Scheme 2: Synthesis of di-tert-butyliminoxyl radical and its decomposition products.
Scheme 3: The proposed reaction pathway of the decomposition of di-tert-butyliminoxyl radical (experimentally...
Scheme 4: Monomolecular decomposition of the tert-butyl(triethylmethyl)oxime radical.
Scheme 5: The synthesis and stability of the most stable dialkyl oxime radicals – di-tert-butyliminoxyl and d...
Scheme 6: The formation of iminoxyl radicals from β-diketones under the action of NO2.
Scheme 7: Synthesis of the diacetyliminoxyl radical.
Scheme 8: Examples of long-living oxime radicals with electron-withdrawing groups and the conditions for thei...
Figure 3: The electronic structure iminoxyl radicals and their geometry compared to the corresponding oximes.
Figure 4: Bond dissociation enthalpies (kcal/mol) of oximes and N,N-disubstituted hydroxylamines calculated o...
Scheme 9: Examples demonstrating the low reactivity of the di-tert-butyliminoxyl radical towards the substrat...
Scheme 10: The reactions of di-tert-butyliminoxyl radical with unsaturated hydrocarbons involving hydrogen ato...
Scheme 11: Possible mechanisms of reaction of di-tert-butyliminoxyl radical with alkenes.
Scheme 12: Products of the reaction between di-tert-butyliminoxyl radical and phenol derivatives.
Scheme 13: The reaction of di-tert-butyliminoxyl radical with amines.
Scheme 14: Reaction of di-tert-butyliminoxyl radicals with organolithium reagents.
Scheme 15: Cross-dehydrogenative C–O coupling of 1,3-dicarbonyl compounds with oximes under the action of mang...
Scheme 16: Cross-dehydrogenative C–O coupling of 1,3-dicarbonyl compounds with oximes under the action of Cu(BF...
Scheme 17: Oxidative C–O coupling of benzylmalononitrile (47) with 3-(hydroxyimino)pentane-2,4-dione (19).
Scheme 18: The proposed mechanism of the oxidative coupling of benzylmalononitrile (47) with diacetyl oxime (19...
Scheme 19: Oxidative C–O coupling of pyrazolones with oximes under the action of Fe(ClO4)3.
Scheme 20: The reaction of diacetyliminoxyl radical with pyrazolones.
Scheme 21: Oxidative C–O coupling of oximes with acetonitrile, ketones, and esters.
Scheme 22: Intramolecular cyclizations of oxime radicals to form substituted isoxazolines or cyclic nitrones.
Scheme 23: TEMPO-mediated oxidative cyclization of oximes with C–H bond cleavage.
Scheme 24: Proposed reaction mechanism of oxidative cyclization of oximes with C–H bond cleavage.
Scheme 25: Selectfluor/Bu4NI-mediated C–H oxidative cyclization of oximes.
Scheme 26: Oxidative cyclization of N-benzyl amidoximes to 1,2,4-oxadiazoles.
Scheme 27: The formation of quinazolinone 73a from 5-phenyl-4,5-dihydro-1,2,4-oxadiazole 74 under air.
Scheme 28: DDQ-mediated oxidative cyclization of thiohydroximic acids.
Scheme 29: Plausible mechanism of the oxidative cyclization of thiohydroximic acids.
Scheme 30: Silver-mediated oxidative cyclization of α-halogenated ketoximes and 1,3-dicarbonyl compounds.
Scheme 31: Possible pathway of one-pot oxidative cyclization of α-halogenated ketoximes and 1,3-dicarbonyl com...
Scheme 32: T(p-F)PPT-catalyzed oxidative cyclization of oximes with the formation of 1,2,4-oxadiazolines.
Scheme 33: Intramolecular cyclization of iminoxyl radicals involving multiple C=C and N=N bonds.
Scheme 34: Oxidative cyclization of β,γ- and γ,δ-unsaturated oximes employing the DEAD or TEMPO/DEAD system wi...
Scheme 35: Cobalt-catalyzed aerobic oxidative cyclization of β,γ-unsaturated oximes.
Scheme 36: Manganese-catalyzed aerobic oxidative cyclization of β,γ-unsaturated oximes.
Scheme 37: Visible light photocatalytic oxidative cyclization of β,γ-unsaturated oximes.
Scheme 38: TBAI/TBHP-mediated radical cascade cyclization of the β,γ-unsaturated oximes.
Scheme 39: TBAI/TBHP-mediated radical cascade cyclization of vinyl isocyanides with β,γ-unsaturated oximes.
Scheme 40: tert-Butylnitrite-mediated oxidative cyclization of unsaturated oximes with the introduction of an ...
Scheme 41: Transformation of unsaturated oxime to oxyiminomethylisoxazoline via the confirmed dimeric nitroso ...
Scheme 42: tert-Butylnitrite-mediated oxidative cyclization of unsaturated oximes with the introduction of a n...
Scheme 43: Synthesis of cyano-substituted oxazolines from unsaturated oximes using the TBN/[RuCl2(p-cymene)]2 ...
Scheme 44: Synthesis of trifluoromethylthiolated isoxazolines from unsaturated oximes.
Scheme 45: Copper-сatalyzed oxidative cyclization of β,γ-unsaturated oximes with the introduction of an azido ...
Scheme 46: TBHP-mediated oxidative cascade cyclization of β,γ-unsaturated oximes and unsaturated N-arylamides.
Scheme 47: Copper-сatalyzed oxidative cyclization of unsaturated oximes with the introduction of an amino grou...
Scheme 48: TEMPO-mediated oxidative cyclization of unsaturated oximes followed by elimination.
Scheme 49: Oxidative cyclization of β,γ-unsaturated oximes with the introduction of a trifluoromethyl group.
Scheme 50: Oxidative cyclization of unsaturated oximes with the introduction of a nitrile group.
Scheme 51: Oxidative cyclization of β,γ-unsaturated oximes to isoxazolines with the introduction of a nitrile ...
Scheme 52: Oxidative cyclization of β,γ-unsaturated oximes to isoxazolines with the introduction of a sulfonyl...
Scheme 53: Oxidative cyclization of β,γ- and γ,δ-unsaturated oximes to isoxazolines with the introduction of a...
Scheme 54: Oxidative cyclization of β,γ-unsaturated oximes to isoxazolines with the introduction of a thiocyan...
Scheme 55: PhI(OAc)2-mediated oxidative cyclization of oximes with C–S and C–Se bond formation.
Scheme 56: PhI(OAc)2-mediated oxidative cyclization of unsaturated oximes accompanied by alkoxylation.
Scheme 57: PhI(OAc)2-mediated cyclization of unsaturated oximes to methylisoxazolines.
Scheme 58: Oxidative cyclization-alkynylation of unsaturated oximes.
Scheme 59: TEMPO-mediated oxidative cyclization of C-glycoside ketoximes to C-glycosylmethylisoxazoles.
Scheme 60: Silver-сatalyzed oxidative cyclization of β,γ-unsaturated oximes with formation of fluoroalkyl isox...
Scheme 61: Oxidative cyclization of β,γ-unsaturated oximes with the formation of haloalkyl isoxazolines.
Scheme 62: Cyclization of β,γ-unsaturated oximes into haloalkyl isoxazolines under the action of the halogenat...
Scheme 63: Synthesis of haloalkyl isoxazoles and cyclic nitrones via oxidative cyclization and 1,2-halogen shi...
Scheme 64: Electrochemical oxidative cyclization of diaryl oximes.
Scheme 65: Copper-сatalyzed cyclization and dioxygenation oximes containing a triple C≡C bond.
Scheme 66: Photoredox-catalyzed sulfonylation of β,γ-unsaturated oximes by sulfonyl hydrazides.
Scheme 67: Oxidative cyclization of β,γ-unsaturated oximes with introduction of sulfonate group.
Scheme 68: Ultrasound-promoted oxidative cyclization of β,γ-unsaturated oximes.
Beilstein J. Org. Chem. 2019, 15, 256–278, doi:10.3762/bjoc.15.23
Graphical Abstract
Scheme 1: The oxidative radical ring-opening/cyclization of cyclopropane derivatives.
Scheme 2: Mn(OAc)3-mediated oxidative radical ring-opening and cyclization of MCPs with malonates.
Scheme 3: Mn(III)-mediated oxidative radical ring-opening and cyclization of MCPs with 1,3-dicarbonyl compoun...
Scheme 4: Heat-promoted ring-opening/cyclization of MCPs with elemental chalgogens.
Scheme 5: Copper(II) acetate-mediated oxidative radical ring-opening and cyclization of MCPs with diphenyl di...
Scheme 6: AIBN-promoted oxidative radical ring-opening and cyclization of MCPs with benzenethiol.
Scheme 7: AIBN-mediated oxidative radical ring-opening and cyclization of MCPs with diethyl phosphites.
Scheme 8: Organic-selenium induced radical ring-opening and cyclization of MCPs derivatives (cyclopropylaldeh...
Scheme 9: Copper(I)-catalyzed oxidative radical trifluoromethylation/ring-opening/cyclization of MCPs with To...
Scheme 10: Ag(I)-mediated trifluoromethylthiolation/ring-opening/cyclization of MCPs with AgSCF3.
Scheme 11: oxidative radical ring-opening and cyclization of MCPs with α-C(sp3)-–H of ethers.
Scheme 12: Oxidative radical ring-opening and cyclization of MCPs with aldehydes.
Scheme 13: Cu(I) or Fe(II)-catalyzed oxidative radical trifluoromethylation/ring-opening/cyclization of MCPs d...
Scheme 14: Rh(II)-catalyzed oxidative radical ring-opening and cyclization of MCPs.
Scheme 15: Ag(I)-catalyzed oxidative radical amination/ring-opening/cyclization of MCPs derivatives.
Scheme 16: Heating-promoted radical ring-opening and cyclization of MCP derivatives (arylvinylidenecyclopropan...
Scheme 17: Bromine radical-mediated ring-opening of alkylidenecyclopropanes.
Scheme 18: Fluoroalkyl (Rf) radical-mediated ring-opening of MCPs.
Scheme 19: Visible-light-induced alkylation/ring-opening/cyclization of cyclopropyl olefins with bromides.
Scheme 20: Mn(III)-mediated ring-opening and [3 + 3]-annulation of cyclopropanols and vinyl azides.
Scheme 21: Ag(I)-catalyzed oxidative ring-opening of cyclopropanols with quinones.
Scheme 22: Ag(I)-catalyzed oxidative ring-opening of cyclopropanols with heteroarenes.
Scheme 23: Cu(I)-catalyzed oxidative ring-opening/trifluoromethylation of cyclopropanols.
Scheme 24: Cu(I)-catalyzed oxidative ring-opening and trifluoromethylation/trifluoromethylthiolation of cyclop...
Scheme 25: Ag(I)-mediated oxidative ring-opening/fluorination of cyclopropanols with Selectfluor.
Scheme 26: Photocatalyzed ring-opening/fluorination of cyclopropanols with Selectfluor.
Scheme 27: Na2S2O8-promoted ring-opening/alkynylation of cyclopropanols with EBX.
Scheme 28: Ag(I)-catalyzed ring-opening and chlorination of cyclopropanols with aldehydes.
Scheme 29: Ag(I)-catalyzed ring-opening/alkynylation of cyclopropanols with EBX.
Scheme 30: Na2S2O8-promoted ring-opening/alkylation of cyclopropanols with acrylamides.
Scheme 31: Cyclopropanol ring-opening initiated tandem cyclization with acrylamides or 2-isocyanobiphenyls.
Scheme 32: Ag(II)-mediated oxidative ring-opening/fluorination of cyclopropanols with AgF2.
Scheme 33: Cu(II)-catalyzed ring-opening/fluoromethylation of cyclopropanols with sulfinate salts.
Scheme 34: Cu(II)-catalyzed ring-opening/sulfonylation of cyclopropanols with sulfinate salts.
Scheme 35: Na2S2O8-promoted ring-opening/arylation of cyclopropanols with propiolamides.
Scheme 36: The ring-opening and [3 + 2]-annulation of cyclopropanols with α,β-unsaturated aldehydes.
Scheme 37: Cu(II)-catalyzed ring-opening/arylation of cyclopropanols with aromatic nitrogen heterocyles.
Scheme 38: Ag(I)-catalyzed ring-opening and difluoromethylthiolation of cyclopropanols with PhSO2SCF2H.
Scheme 39: Ag(I)-catalyzed ring-opening and acylation of cyclopropanols with aldehydes.
Scheme 40: Aerobic oxidation ring-opening of cyclopropanols for the synthesis of 2-oxyranyl ketones.
Scheme 41: Aerobic oxidation ring-opening of cyclopropanols for the synthesis of linear enones.
Scheme 42: Aerobic oxidation ring-opening of cyclopropanols for the synthesis of metabolite.
Beilstein J. Org. Chem. 2018, 14, 1203–1207, doi:10.3762/bjoc.14.101
Graphical Abstract
Scheme 1: Mechanistic hypothesis.
Scheme 2: Extension of the method.
Scheme 3: Carbon-based nucleophiles.
Scheme 4: THF ring opening.
Beilstein J. Org. Chem. 2018, 14, 54–83, doi:10.3762/bjoc.14.4
Graphical Abstract
Scheme 1: General overview over the sulfur-based substrates and reactive intermediates that are discussed in ...
Scheme 2: Photoredox-catalyzed radical thiol–ene reaction, applying [Ru(bpz)3](PF6)2 as photocatalyst.
Scheme 3: Photoredox-catalyzed thiol–ene reaction of aliphatic thiols with alkenes enabled by aniline derivat...
Scheme 4: Photoredox-catalyzed radical thiol–ene reaction for the postfunctionalization of polymers (a) and n...
Scheme 5: Photoredox-catalyzed thiol–ene reaction enabled by bromotrichloromethane as redox additive.
Scheme 6: Photoredox-catalyzed preparation of β-ketosulfoxides with Eosin Y as organic dye as photoredox cata...
Scheme 7: Greaney’s photocatalytic radical thiol–ene reaction, applying TiO2 nanoparticles as photocatalyst.
Scheme 8: Fadeyi’s photocatalytic radical thiol–ene reaction, applying Bi2O3 as photocatalyst.
Scheme 9: Ananikov’s photocatalytic radical thiol-yne reaction, applying Eosin Y as photocatalyst.
Scheme 10: Organocatalytic visible-light photoinitiated thiol–ene coupling, applying phenylglyoxylic acid as o...
Scheme 11: Xia’s photoredox-catalyzed synthesis of 2,3-disubstituted benzothiophenes, applying 9-mesityl-10-me...
Scheme 12: Wang’s metal-free photoredox-catalyzed radical thiol–ene reaction, applying 9-mesityl-10-methylacri...
Scheme 13: Visible-light benzophenone-catalyzed metal- and oxidant-free radical thiol–ene reaction.
Scheme 14: Visible-light catalyzed C-3 sulfenylation of indole derivatives using Rose Bengal as organic dye.
Scheme 15: Photocatalyzed radical thiol–ene reaction and subsequent aerobic sulfide-oxidation with Rose Bengal...
Scheme 16: Photoredox-catalyzed synthesis of diaryl sulfides.
Scheme 17: Photocatalytic cross-coupling of aryl thiols with aryl diazonium salts, using Eosin Y as photoredox...
Scheme 18: Photocatalyzed cross-coupling of aryl diazonium salts with cysteines in batch and in a microphotore...
Scheme 19: Fu’s [Ir]-catalyzed photoredox arylation of aryl thiols with aryl halides.
Scheme 20: Fu’s photoredox-catalyzed difluoromethylation of aryl thiols.
Scheme 21: C–S cross-coupling of thiols with aryl iodides via [Ir]-photoredox and [Ni]-dual-catalysis.
Scheme 22: C–S cross-coupling of thiols with aryl bromides, applying 3,7-bis-(biphenyl-4-yl)-10-(1-naphthyl)ph...
Scheme 23: Collin’s photochemical dual-catalytic cross-coupling of thiols with bromoalkynes.
Scheme 24: Visible-light-promoted C–S cross-coupling via intermolecular electron donor–acceptor complex format...
Scheme 25: Li’s visible-light photoredox-catalyzed thiocyanation of indole derivatives with Rose Bengal as pho...
Scheme 26: Hajra’s visible-light photoredox-catalyzed thiocyanation of imidazoheterocycles with Eosin Y as pho...
Scheme 27: Wang’s photoredox-catalyzed thiocyanation reaction of indoles, applying heterogeneous TiO2/MoS2 nan...
Scheme 28: Yadav’s photoredox-catalyzed α-C(sp3)–H thiocyanation reaction for tertiary amines, applying Eosin ...
Scheme 29: Yadav’s photoredox-catalyzed synthesis of 5-aryl-2-imino-1,3-oxathiolanes.
Scheme 30: Yadav’s photoredox-catalyzed synthesis of 1,3-oxathiolane-2-thiones.
Scheme 31: Li’s photoredox catalysis for the preparation of 2-substituted benzothiazoles, applying [Ru(bpy)3](...
Scheme 32: Lei’s external oxidant-free synthesis of 2-substituted benzothiazoles by merging photoredox and tra...
Scheme 33: Metal-free photocatalyzed synthesis of 2-aminobenzothiazoles, applying Eosin Y as photocatalyst.
Scheme 34: Metal-free photocatalyzed synthesis of 1,3,4-thiadiazoles, using Eosin Y as photocatalyst.
Scheme 35: Visible-light photoredox-catalyzed preparation of benzothiophenes with Eosin Y.
Scheme 36: Visible-light-induced KOH/DMSO superbase-promoted preparation of benzothiophenes.
Scheme 37: Jacobi von Wangelin’s photocatalytic approach for the synthesis of aryl sulfides, applying Eosin Y ...
Scheme 38: Visible-light photosensitized α-C(sp3)–H thiolation of aliphatic ethers.
Scheme 39: Visible-light photocatalyzed cross-coupling of alkyl and aryl thiosulfates with aryl diazonium salt...
Scheme 40: Visible-light photocatalyzed, controllable sulfenylation and sulfoxidation with organic thiosulfate...
Scheme 41: Rastogi’s photoredox-catalyzed methylsulfoxidation of aryl diazonium salts, using [Ru(bpy)3]Cl2 as ...
Scheme 42: a) Visible-light metal-free Eosin Y-catalyzed procedure for the preparation of vinyl sulfones from ...
Scheme 43: Visible-light photocatalyzed cross-coupling of sodium sulfinates with secondary enamides.
Scheme 44: Wang’s photocatalyzed oxidative cyclization of phenyl propiolates with sulfinic acids, applying Eos...
Scheme 45: Lei’s sacrificial oxidant-free synthesis of allyl sulfones by merging photoredox and transition met...
Scheme 46: Photocatalyzed Markovnikov-selective radical/radical cross-coupling of aryl sulfinic acids and term...
Scheme 47: Visible-light Eosin Y induced cross-coupling of aryl sulfinic acids and styrene derivatives, afford...
Scheme 48: Photoredox-catalyzed bicyclization of 1,7-enynes with sulfinic acids, applying Eosin Y as photocata...
Scheme 49: Visible-light-accelerated C–H-sulfinylation of arenes and heteroarenes.
Scheme 50: Visible-light photoredox-catalyzed β-selenosulfonylation of electron-rich olefins, applying [Ru(bpy)...
Scheme 51: Photocatalyzed preparation of β-chlorosulfones from the respective olefins and p-toluenesulfonyl ch...
Scheme 52: a) Photocatalyzed preparation of β-amidovinyl sulfones from sulfonyl chlorides. b) Preparation of β...
Scheme 53: Visible-light photocatalyzed sulfonylation of aliphatic tertiary amines, applying [Ru(bpy)3](PF6)2 ...
Scheme 54: Reiser’s visible-light photoredox-catalyzed preparation of β-hydroxysulfones from sulfonyl chloride...
Scheme 55: a) Sun’s visible-light-catalyzed approach for the preparation of isoquinolinonediones, applying [fac...
Scheme 56: Visible-light photocatalyzed sulfonylation/cyclization of vinyl azides, applying [Ru(bpy)3]Cl2 as p...
Scheme 57: Visible-light photocatalyzed procedure for the formation of β-ketosulfones from aryl sulfonyl chlor...
Scheme 58: Zheng’s method for the sulfenylation of indole derivatives, applying sulfonyl chlorides via visible...
Scheme 59: Cai’s visible-light induced synthesis of β-ketosulfones from sulfonyl hydrazines and alkynes.
Scheme 60: Photoredox-catalyzed approach for the preparation of vinyl sulfones from sulfonyl hydrazines and ci...
Scheme 61: Jacobi von Wangelin’s visible-light photocatalyzed chlorosulfonylation of anilines.
Scheme 62: Three-component photoredox-catalyzed synthesis of N-amino sulfonamides, applying PDI as organic dye....
Scheme 63: Visible-light induced preparation of complex sulfones from oximes, silyl enol ethers and SO2.