Search for "radical-mediated" in Full Text gives 52 result(s) in Beilstein Journal of Organic Chemistry.
Beilstein J. Org. Chem. 2020, 16, 384–390, doi:10.3762/bjoc.16.36
Graphical Abstract
Scheme 1: A high yielding, highly selective room-temperature direct arylation reaction between indole and iod...
Figure 1: 1H NMR (500 MHz, CDCl3) of (a) 5-iodo-1-octylindole monomer (b) PIn prepared according to condition...
Figure 2: MALDI–TOF MS of PIn, indicating octylindole repeat units with three different types of end groups. ...
Scheme 2: Commonly discussed mechanisms for C2 selective direct arylation, none containing radical intermedia...
Scheme 3: Proposed mechanism for palladium radical involved reaction between indole and iodobenzene.
Scheme 4: Radical trap effects on literature methods for the direct arylation at room temperature. A) From re...
Beilstein J. Org. Chem. 2020, 16, 248–280, doi:10.3762/bjoc.16.26
Graphical Abstract
Figure 1: List of photoredox catalysts used for C–H bond functionalizations.
Figure 2: List of metal-based photoredox catalysts used in this review article.
Figure 3: Jablonski diagram.
Figure 4: Photoredox catalysis via reductive or oxidative pathways. D = donor, A = acceptor, S = substrate, P...
Figure 5: Schematic representation of the combination of photoredox catalysis and transition metal catalysis.
Scheme 1: Weinreb amide C–H olefination.
Figure 6: Mechanism for the formation of 21 from 19 using photoredox catalyst 11.
Scheme 2: C–H olefination of phenolic ethers.
Scheme 3: Decarboxylative acylation of acetanilides.
Figure 7: Mechanism for the formation of 30 from acetanilide derivatives.
Scheme 4: Synthesis of fluorenone derivatives by intramolecular deoxygenative acylation of biaryl carboxylic ...
Figure 8: Mechanism for the photoredox-catalyzed synthesis of fluorenone derivatives.
Scheme 5: Synthesis of benzothiazoles via aerobic C–H thiolation.
Figure 9: Plausible mechanism for the construction of benzothiazoles from benzothioamides.
Scheme 6: Synthesis of benzothiazoles via oxidant-free C–H thiolation.
Figure 10: Mechanism involved in the synthesis of benzothiazoles via oxidant-free C–H thiolation.
Scheme 7: Synthesis of indoles via C–H cyclization of anilides with alkynes.
Scheme 8: Preparation of 3-trifluoromethylcoumarins via C–H cyclization of arylpropiolate esters.
Figure 11: Mechanistic pathway for the synthesis of coumarin derivatives via C–H cyclization.
Scheme 9: Monobenzoyloxylation without chelation assistance.
Figure 12: Plausible mechanism for the formation of 71 from 70.
Scheme 10: Aryl-substituted arenes prepared by inorganic photoredox catalysis using 12a.
Figure 13: Proposed mechanism for C–H arylations in the presence of 12a and a Pd catalyst.
Scheme 11: Arylation of purines via dual photoredox catalysis.
Scheme 12: Arylation of substituted arenes with an organic photoredox catalyst.
Scheme 13: C–H trifluoromethylation.
Figure 14: Proposed mechanism for the trifluoromethylation of 88.
Scheme 14: Synthesis of benzo-3,4-coumarin derivatives.
Figure 15: Plausible mechanism for the synthesis of substituted coumarins.
Scheme 15: Oxidant-free oxidative phosphonylation.
Figure 16: Mechanism proposed for the phosphonylation reaction of 100.
Scheme 16: Nitration of anilines.
Figure 17: Plausible mechanism for the nitration of aniline derivatives via photoredox catalysis.
Scheme 17: Synthesis of carbazoles via intramolecular amination.
Figure 18: Proposed mechanism for the formation of carbazoles from biaryl derivatives.
Scheme 18: Synthesis of substituted phenols using QuCN.
Figure 19: Mechanism for the synthesis of phenol derivatives with photoredox catalyst 8.
Scheme 19: Synthesis of substituted phenols with DDQ (5).
Figure 20: Possible mechanism for the generation of phenols with the aid of photoredox catalyst 5.
Scheme 20: Aerobic bromination of arenes using an acridinium-based photocatalyst.
Scheme 21: Aerobic bromination of arenes with anthraquinone.
Figure 21: Proposed mechanism for the synthesis of monobrominated compounds.
Scheme 22: Chlorination of benzene derivatives with Mes-Acr-MeClO4 (2).
Figure 22: Mechanism for the synthesis of 131 from 132.
Scheme 23: Chlorination of arenes with 4CzIPN (5a).
Figure 23: Plausible mechanism for the oxidative photocatalytic monochlorination using 5a.
Scheme 24: Monofluorination using QuCN-ClO4 (8).
Scheme 25: Fluorination with fluorine-18.
Scheme 26: Aerobic amination with acridinium catalyst 3a.
Figure 24: Plausible mechanism for the aerobic amination using acridinium catalyst 3a.
Scheme 27: Aerobic aminations with semiconductor photoredox catalyst 18.
Scheme 28: Perfluoroalkylation of arenes.
Scheme 29: Synthesis of benzonitriles in the presence of 3a.
Figure 25: Plausible mechanism for the synthesis of substituted benzonitrile derivatives in the presence of 3a....
Beilstein J. Org. Chem. 2019, 15, 2710–2746, doi:10.3762/bjoc.15.264
Graphical Abstract
Figure 1: General classification of asymmetric electroorganic reactions.
Scheme 1: Asymmetric reduction of 4-acetylpyridine using a modified graphite cathode.
Scheme 2: Asymmetric hydrogenation of ketones using Raney nickel powder electrodes modified with optically ac...
Scheme 3: Asymmetric reduction of prochiral activated olefins with a poly-ʟ-valine-coated graphite cathode.
Scheme 4: Asymmetric reduction of prochiral carbonyl compounds, oximes and gem-dibromides on a poly-ʟ-valine-...
Scheme 5: Asymmetric hydrogenation of prochiral ketones with poly[RuIII(L)2Cl2]+-modified carbon felt cathode...
Scheme 6: Asymmetric hydrogenation of α-keto esters using chiral polypyrrole film-coated cathode incorporated...
Scheme 7: Quinidine and cinchonidine alkaloid-induced asymmetric electroreduction of acetophenone.
Scheme 8: Asymmetric electroreduction of 4- and 2-acetylpyridines at a mercury cathode in the presence of a c...
Scheme 9: Enantioselective reduction of 4-methylcoumarin in the presence of catalytic yohimbine.
Scheme 10: Cinchonine-induced asymmetric electrocarboxylation of 4-methylpropiophenone.
Scheme 11: Enantioselective hydrogenation of methyl benzoylformate using an alkaloid entrapped silver cathode.
Scheme 12: Alkaloid-induced enantioselective hydrogenation using a Cu nanoparticle cathode.
Scheme 13: Alkaloid-induced enantioselective hydrogenation of aromatic ketones using a bimetallic Pt@Cu cathod...
Scheme 14: Enantioselective reduction of ketones at mercury cathode using N,N'-dimethylquininium tetrafluorobo...
Scheme 15: Asymmetric synthesis of an amino acid using an electrode modified with amino acid oxidase and elect...
Scheme 16: Asymmetric oxidation of p-tolyl methyl sulfide using chemically modified graphite anode.
Scheme 17: Asymmetric oxidation of unsymmetric sulfides using poly(amino acid)-coated electrodes.
Scheme 18: Enantioselective, electocatalytic oxidative coupling on TEMPO-modified graphite felt electrode in t...
Scheme 19: Asymmetric electrocatalytic oxidation of racemic alcohols on a TEMPO-modified graphite felt electro...
Scheme 20: Asymmetric electrocatalytic lactonization of diols on TEMPO-modified graphite felt electrodes.
Scheme 21: Asymmetric electrochemical pinacolization in a chiral solvent.
Scheme 22: Asymmetric electroreduction using a chiral supporting electrolyte.
Scheme 23: Asymmetric anodic oxidation of enol acetates using chiral supporting electrolytes.
Scheme 24: Kinetic resolution of primary amines using a chiral N-oxyl radical mediator.
Scheme 25: Chiral N-oxyl-radical-mediated kinetic resolution of secondary alcohols via electrochemical oxidati...
Scheme 26: Chiral iodoarene-mediated asymmetric electrochemical lactonization.
Scheme 27: Os-catalyzed electrochemical asymmetric dihydroxylation of olefins using the Sharpless ligand and i...
Scheme 28: Asymmetric electrochemical epoxidation of olefins catalyzed by a chiral Mn-salen complex.
Scheme 29: Asymmetric electrooxidation of 1,2-diols, and amino alcohols using a chiral copper catalyst.
Scheme 30: Mechanism of asymmetric electrooxidation of 1,2-diols, and amino alcohols using a chiral copper cat...
Scheme 31: Enantioselective electrocarboxylation catalyzed by an electrogenerated chiral [CoI(salen)]− complex....
Scheme 32: Asymmetric oxidative cross coupling of 2-acylimidazoles with silyl enol ethers.
Scheme 33: Ni-catalyzed asymmetric electroreductive cleavage of allylic β-keto ester 89.
Scheme 34: Asymmetric alkylation using a combination of electrosynthesis and a chiral Ni catalyst.
Scheme 35: Mechanism of asymmetric alkylation using a combination of electrosynthesis and a chiral Ni catalyst....
Scheme 36: Asymmetric epoxidation by electrogenerated percarbonate and persulfate ions in the presence of chir...
Scheme 37: α-Oxyamination of aldehydes via anodic oxidation catalyzed by chiral secondary amines.
Scheme 38: The α-alkylation of aldehydes via anodic oxidation catalyzed by chiral secondary amines.
Scheme 39: Mechanism of α-alkylation of aldehydes via anodic oxidation catalyzed by chiral secondary amines.
Scheme 40: Electrochemical chiral secondary amine-catalyzed intermolecular α-arylation of aldehydes.
Scheme 41: Mechanism of electrochemical chiral secondary amine-catalyzed intermolecular α-arylation of aldehyd...
Scheme 42: Asymmetric cross-dehydrogenative coupling of tertiary amines with simple ketones via an electrochem...
Scheme 43: Electroenzymatic asymmetric reduction using enoate reductase.
Scheme 44: Assymetric reduction using alcohol dehydrogenase as the electrocatalyst.
Scheme 45: Asymmetric electroreduction catalyzed by thermophilic NAD-dependent alcohol dehydrogenase.
Scheme 46: Asymmetric epoxidation of styrene by electrochemical regeneration of flavin-dependent monooxygenase....
Scheme 47: Asymmetric electroreduction using a chloroperoxidase catalyst.
Scheme 48: Asymmetric electrochemical transformation mediated by hydrophobic vitamin B12.
Scheme 49: Diastereoselective cathodic reduction of phenylglyoxalic acids substituted with amines as chiral au...
Scheme 50: Ni-catalyzed asymmetric electroreductive cross coupling of aryl halides with α-chloropropanoic acid...
Scheme 51: Electrochemical Mannich addition of silyloxyfuran to in situ-generated N-acyliminium ions.
Scheme 52: Stereoselective electroreductive homodimerization of cinnamates attached to a camphor-derived chira...
Scheme 53: Diastereoselective electrochemical carboxylation of chiral α-bromocarboxylic acid derivatives.
Scheme 54: Electrocatalytic stereoselective conjugate addition of chiral β-dicarbonyl compounds to methyl viny...
Scheme 55: Stereoselective electrochemical carboxylation of chiral cinnamic acid derivatives under a CO2 atmos...
Scheme 56: Electrochemical diastereoselective α-alkylation of pyrrolidines attached with phosphorus-derived ch...
Scheme 57: Electrogenerated cyanomethyl anion-induced synthesis of chiral cis-β-lactams from amides bearing ch...
Scheme 58: Diastereoselective anodic oxidation followed by intramolecular cyclization of ω-hydroxyl amides bea...
Scheme 59: Electrochemical deprotonation of Ni(II) glycinate containing (S)-BPB as a chiral auxiliary: diaster...
Scheme 60: Enantioselective electroreductive coupling of diaryl ketones with α,β-unsaturated carbonyl compound...
Scheme 61: Asymmetric total synthesis of ropivacaine and its analogues using a electroorganic reaction as a ke...
Scheme 62: Asymmetric total synthesis of (−)-crispine A and its natural enantiomer via anodic cyanation of tet...
Scheme 63: Asymmetric oxidative electrodimerization of cinnamic acid derivatives as key step for the synthesis...
Beilstein J. Org. Chem. 2019, 15, 2213–2270, doi:10.3762/bjoc.15.218
Graphical Abstract
Scheme 1: The main three strategies of fluorination: nucleophilic, electrophilic and radical fluorination.
Scheme 2: Doyle’s Pd-catalyzed fluorination of allylic chlorides.
Scheme 3: Allylic fluorination of 2- and 3-substituted propenyl esters.
Scheme 4: Regioselective allylic fluorination of cinnamyl phosphorothioate esters.
Scheme 5: Palladium-catalyzed aliphatic C–H fluorination reported by Doyle.
Scheme 6: Pd-catalyzed enantioselective fluorination of α-ketoesters followed by stereoselective reduction to...
Scheme 7: Pd-catalyzed C(sp3)–H fluorination of oxindoles.
Scheme 8: C–H fluorination of 8-methylquinoline derivatives with F− reagents.
Scheme 9: Fluorination of α-cyano acetates reported by van Leeuwen.
Scheme 10: The catalytic enantioselective electrophilic C–H fluorination of α-chloro-β-keto phosphonates.
Scheme 11: Fluorination of unactivated C(sp3)–H bonds directed by the bidentate PIP auxiliary.
Scheme 12: Fluorination of C(sp3)–H bonds at the β-position of carboxylic acids.
Scheme 13: Enantioselective benzylic C–H fluorination with a chiral transient directing group.
Scheme 14: Microwave-heated Pd-catalyzed fluorination of aryl alcohols.
Scheme 15: Fluorination of aryl potassium trifluoroborates.
Scheme 16: C(sp2)–F bond formation using precatalyst [L·Pd]2(cod).
Scheme 17: Pd-catalyzed fluorination of (hetero)aryl triflates and bromides.
Scheme 18: The Pd-catalyzed C–H fluorination of arenes with Selectfluor/NFSI.
Scheme 19: Pd(II)-catalyzed ortho-monofluorination protocol for benzoic acids.
Scheme 20: Pd-catalyzed C(sp2)–H bond fluorination of 2-arylbenzothiazoles.
Scheme 21: Nitrate-promoted fluorination of aromatic and olefinic C(sp2)–H bonds and proposed mechanism.
Scheme 22: Fluorination of oxalyl amide-protected benzylamine derivatives.
Scheme 23: C–H fluorination of benzaldehydes with orthanilic acids as transient directing group.
Scheme 24: Pd(II)-catalyzed aryl C–H fluorination with various directing groups.
Scheme 25: Cu-catalyzed aliphatic, allylic, and benzylic fluorination.
Scheme 26: Cu-catalyzed SN2 fluorination of primary and secondary alkyl bromides.
Scheme 27: Copper-catalyzed fluorination of alkyl triflates.
Scheme 28: Cu-catalyzed fluorination of allylic bromides and chlorides.
Scheme 29: Synthetic strategy for the fluorination of active methylene compounds.
Scheme 30: Fluorination of β-ketoesters using a tartrate-derived bidentate bisoxazoline-Cu(II) complex.
Scheme 31: Highly enantioselective fluorination of β-ketoesters and N-Boc-oxindoles.
Scheme 32: Amide group-assisted site-selective fluorination of α-bromocarbonyl compounds.
Scheme 33: Cu-mediated aryl fluorination reported by Sanford [77].
Scheme 34: Mono- or difluorination reactions of benzoic acid derivatives.
Scheme 35: Cu-catalyzed fluorination of diaryliodonium salts with KF.
Scheme 36: Copper(I)-catalyzed cross-coupling of 2-pyridylaryl bromides.
Scheme 37: AgNO3-catalyzed decarboxylative fluorination of aliphatic carboxylic acids.
Scheme 38: The Mn-catalyzed aliphatic and benzylic C–H fluorination.
Scheme 39: Iron(II)-promoted C–H fluorination of benzylic substrates.
Scheme 40: Ag-catalyzed fluorodecarboxylation of carboxylic acids.
Scheme 41: Vanadium-catalyzed C(sp3)–H fluorination.
Scheme 42: AgNO3-catalyzed radical deboronofluorination of alkylboronates and boronic acids.
Scheme 43: Selective heterobenzylic C–H fluorination with Selectfluor reported by Van Humbeck.
Scheme 44: Fe(II)-catalyzed site-selective fluorination guided by an alkoxyl radical.
Scheme 45: Fluorination of allylic trichloroacetimidates reported by Nguyen et al.
Scheme 46: Iridium-catalyzed fluorination of allylic carbonates with TBAF(t-BuOH)4.
Scheme 47: Iridium-catalyzed asymmetric fluorination of allylic trichloroacetimidates.
Scheme 48: Cobalt-catalyzed α-fluorination of β-ketoesters.
Scheme 49: Nickel-catalyzed α-fluorination of various α-chloro-β-ketoesters.
Scheme 50: Ni(II)-catalyzed enantioselective fluorination of oxindoles and β-ketoesters.
Scheme 51: Scandium(III)-catalyzed asymmetric C–H fluorination of unprotected 3-substituted oxindoles.
Scheme 52: Iron-catalyzed directed C–H fluorination.
Scheme 53: Electrophilic silver-catalyzed Ar–F bond-forming reaction from arylstannanes.
Figure 1: Nucleophilic, electrophilic and radical CF3 sources.
Scheme 54: Cu(I)-catalyzed allylic trifluoromethylation of unactivated terminal olefins.
Scheme 55: Direct copper-catalyzed trifluoromethylation of allylsilanes.
Scheme 56: Cupper-catalyzed enantioselective trifluoromethylation of five and six-membered ring β-ketoesters.
Scheme 57: Cu-catalyzed highly stereoselective trifluoromethylation of secondary propargyl sulfonates.
Scheme 58: Remote C(sp3)–H trifluoromethylation of carboxamides and sulfonamides.
Scheme 59: Trifluoromethylation of allylsilanes with photoredox catalysis.
Scheme 60: Ag-catalyzed decarboxylative trifluoromethylation of aliphatic carboxylic acids in aqueous CH3CN.
Scheme 61: Decarboxylative trifluoromethylation of aliphatic carboxylic acids via combined photoredox and copp...
Scheme 62: Palladium-catalyzed Ar–CF3 bond-forming reaction.
Scheme 63: Palladium-catalyzed trifluoromethylation of arenes with diverse heterocyclic directing groups.
Scheme 64: Pd-catalyzed trifluoromethylation of indoles as reported by Liu.
Scheme 65: Pd-catalyzed trifluoromethylation of vinyl triflates and vinyl nonaflates.
Scheme 66: Pd(II)-catalyzed ortho-trifluoromethylation of aromatic C–H bonds.
Scheme 67: Visible-light-induced Pd(OAc)2-catalyzed ortho-trifluoromethylation of acetanilides with CF3SO2Na.
Scheme 68: CuI-catalyzed trifluoromethylation of aryl- and alkenylboronic acids.
Scheme 69: Cu-catalyzed trifluoromethylation of aryl- and vinylboronic acids.
Scheme 70: Copper-catalyzed trifluoromethylation of α,β-unsaturated carboxylic acids.
Scheme 71: Formation of C(sp2)–CF3 bond catalyzed by copper(I) complex.
Scheme 72: Loh’s Cu(I)-catalyzed trifluoromethylation of enamides and electron-deficient alkenes.
Scheme 73: Copper and iron-catalyzed decarboxylative tri- and difluoromethylation.
Scheme 74: Cu-catalyzed trifluoromethylation of hydrazones developed by Bouyssi.
Scheme 75: Cu(I)-catalyzed trifluoromethylation of terminal alkenes.
Scheme 76: Cu/Ag-catalyzed decarboxylative trifluoromethylation of cinnamic acids.
Scheme 77: Copper-catalyzed direct alkenyl C–H trifluoromethylation.
Scheme 78: Copper(I/II)-catalyzed direct trifluoromethylation of styrene derivatives.
Scheme 79: Regioselective trifluoromethylation of pivalamido arenes and heteroarenes.
Scheme 80: Synthesis of trifluoromethylquinones in the presence of copper(I).
Scheme 81: Oxidative trifluoromethylation of imidazoheterocycles in ionic liquid/water.
Scheme 82: A mild and fast continuous-flow trifluoromethylation of coumarins using a CuI/CF3SO2Na/TBHP system.
Scheme 83: Copper-catalyzed oxidative trifluoromethylation of various 8-aminoquinolines.
Scheme 84: PA-directed copper-catalyzed trifluoromethylation of anilines.
Scheme 85: Trifluoromethylation of potassium vinyltrifluoroborates catalyzed by Fe(II).
Scheme 86: Alkenyl trifluoromethylation catalyzed by Ru(phen)3Cl2 as photocatalyst.
Scheme 87: Ru-catalyzed trifluoromethylation of alkenes by Akita’s group.
Scheme 88: Ir-catalyzed Cvinyl–CF3 bond formation of α,β-unsaturated carboxylic acids.
Scheme 89: Ag(I)-catalyzed denitrative trifluoromethylation of β-nitrostyrenes.
Scheme 90: Photocatalyzed direct trifluoromethylation of aryl and heteroaryl C–H bonds.
Scheme 91: Rhenium (MTO)-catalyzed direct trifluoromethylation of aromatic substrates.
Scheme 92: Trifluoromethylation of unprotected anilines under [Ir(ppy)3] catalyst.
Scheme 93: Oxidative trifluoromethylation of imidazopyridines and imidazoheterocycles.
Scheme 94: Ruthenium-catalyzed trifluoromethylation of (hetero)arenes with trifluoroacetic anhydride.
Scheme 95: Phosphovanadomolybdic acid-catalyzed direct C–H trifluoromethylation.
Scheme 96: Picolinamide-assisted ortho-trifluoromethylation of arylamines.
Scheme 97: A nickel-catalyzed C–H trifluoromethylation of free anilines.
Scheme 98: Cu-mediated trifluoromethylation of terminal alkynes reported by Qing.
Scheme 99: Huang’s C(sp)–H trifluoromethylation using Togni’s reagent.
Scheme 100: Cu-catalyzed methods for trifluoromethylation with Umemoto’s reagent.
Scheme 101: The synthesis of alkynyl-CF3 compounds in the presence of fac-[Ir(ppy)3] under visible-light irradi...
Scheme 102: Pd-catalyzed Heck reaction reported by Reutrakul.
Scheme 103: Difluoromethylation of enamides and ene-carbamates.
Scheme 104: Difluoromethylation of α,β-unsaturated carboxylic acids.
Scheme 105: Copper-catalyzed direct C(sp2)–H difluoroacetylation reported by Pannecoucke and co-workers.
Scheme 106: Difluoroalkylation of aldehyde-derived hydrazones with functionalized difluoromethyl bromides.
Scheme 107: Photoredox-catalyzed C–H difluoroalkylation of aldehyde-derived hydrazones.
Scheme 108: Synergistic ruthenium(II)-catalyzed C–H difluoromethylation reported by Ackermann.
Scheme 109: Visible-light photocatalytic decarboxylation of α,β-unsaturated carboxylic acids.
Scheme 110: Synthesis of difluorinated ketones via S-alkyl dithiocarbamates obtained from acyl chlorides and po...
Scheme 111: Synthesis of aryl and heteroaryl difluoromethylated phosphonates.
Scheme 112: Difluoroalkylation of secondary propargyl sulfonates using Cu as the catalyst.
Scheme 113: Ru(II)-mediated para-selective difluoromethylation of anilides and their derivatives.
Scheme 114: Bulky diamine ligand promoted cross-coupling of difluoroalkyl bromides.
Scheme 115: Copper-catalyzed C3–H difluoroacetylation of quinoxalinones.
Scheme 116: Copper(I) chloride-catalyzed trifluoromethylthiolation of enamines, indoles and β-ketoesters.
Scheme 117: Copper-boxmi-catalyzed asymmetric trifluoromethylthiolation of β-ketoesters.
Scheme 118: Direct Cu-catalyzed trifluoromethylthiolation of boronic acids and alkynes.
Scheme 119: Cu-catalyzed synthesis of α-trifluoromethylthio-substituted ketones.
Scheme 120: Trifluoromethylthiolation reactions promoted by diazotriflone and copper.
Scheme 121: Halide activation of N-(trifluoromethylthio)phthalimide.
Scheme 122: The visible light-promoted trifluoromethylthiolation reported by Glorius.
Scheme 123: Synthesis of α-trifluoromethylthioesters via Goossen’s approach.
Scheme 124: Photoinduced trifluoromethylthiolation of diazonium salts.
Scheme 125: Ag-mediated trifluoromethoxylation of aryl stannanes and arylboronic acids.
Scheme 126: Catalytic (hetero)aryl C–H trifluoromethoxylation under visible light.
Scheme 127: Photoinduced C–H-bond trifluromethoxylation of (hetero)arenes.
Beilstein J. Org. Chem. 2019, 15, 1822–1828, doi:10.3762/bjoc.15.176
Graphical Abstract
Scheme 1: Concept: Alkene difuctionalization by four-component radical reaction using xanthates, alkenes, CO ...
Figure 1: Vicinal difunctionalization of alkenes by four-component radical cascade reaction using xanthogenat...
Figure 2: Proposed radical chain mechanism.
Beilstein J. Org. Chem. 2019, 15, 937–946, doi:10.3762/bjoc.15.90
Graphical Abstract
Figure 1: Structure of the β-thiols 1a and 1b and of the commercial alkenes 2a and 2b.
Scheme 1: Synthesis of the n-alkyl thioglycosides 3–5, 7 and 8. Detailed reaction conditions are reported in ...
Scheme 2: Synthesis of the lipophilic scaffold 6; DMAP = N,N-dimethylaminopyridine.
Figure 2: Periodic monitoring by 1H NMR (300 MHz, DMF-d7) of the formation of product 8 from a mixture compou...
Figure 3: Micrographs of giant vesicles and lipid aggregates obtained from the gentle hydration (in PBS, pH 7...
Figure 4: A simplified (and not in scale) representation of the ELLA assay, to study the interaction between ...
Figure 5:
Inhibition curves for the binding of WGA-HRP to PAA-GlcNAc by D-GlcNAc The symbols (■), () and (○) ...
Figure 6: Main poses obtained from docking experiments. WGA (PDB 2UVO) surface is shown in white for monomer ...
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, 2553–2567, doi:10.3762/bjoc.14.232
Graphical Abstract
Figure 1: (a) Structure and (b) reactivity of B12.
Figure 2: (a) Schematic representation of B12 enzyme-involving systems. (b) Construction of biomimetic and bi...
Scheme 1: (a) Carbon-skeleton rearrangement mediated by a coenzyme B12-depenedent enzyme. (b) Electrochemical...
Scheme 2: Electrochemical carbon-skeleton arrangements mediated by B12 model complexes.
Figure 3: Key electrochemical reactivity of 1 and 2 in methylated forms.
Scheme 3: Carbon-skeleton arrangements mediated by B12-vesicle artificial enzymes.
Scheme 4: Carbon-skeleton arrangements mediated by B12-HSA artificial enzymes.
Scheme 5: Photochemical carbon-skeleton arrangements mediated by B12-Ru@MOF.
Scheme 6: (a) Methyl transfer reaction mediated by B12-dependent methionine synthase. (b) Methyl transfer rea...
Scheme 7: Methyl transfer reaction for the detoxification of inorganic arsenics.
Scheme 8: (a) Dechlorination of 1,1,2,2-tetrarchloroethene mediated by a reductive dehalogenase. (b) Electroc...
Scheme 9: Visible-light-driven dechlorination of DDT using 1 in the presence of photosensitizers.
Scheme 10: 1,2-Migration of a phenyl group mediated by the visible-light-driven catalytic system composed of 1...
Scheme 11: Ring-expansion reactions mediated by the B12-TiO2 hybrid catalyst with UV-light irradiation.
Scheme 12: Trifluoromethylation and perfluoroalkylation of aromatic compounds achieved through electrolysis wi...
Beilstein J. Org. Chem. 2018, 14, 1668–1692, doi:10.3762/bjoc.14.143
Graphical Abstract
Figure 1: Some sulfur-containing natural products.
Figure 2: Some natural products incorporating β-hydroxy sulfide moieties.
Figure 3: Some synthetic β-hydroxy sulfides of clinical value.
Scheme 1: Alumina-mediated synthesis of β-hydroxy sulfides, ethers, amines and selenides from epoxides.
Scheme 2: β-Hydroxy sulfide syntheses by ring opening of epoxides under different Lewis and Brønsted acid and...
Scheme 3: n-Bu3P-catalyzed thiolysis of epoxides and aziridines to provide the corresponding β-hydroxy and β-...
Scheme 4: Zinc(II) chloride-mediated thiolysis of epoxides.
Scheme 5: Thiolysis of epoxides and one-pot oxidation to β-hydroxy sulfoxides under microwave irradiation.
Scheme 6: Gallium triflate-catalyzed ring opening of epoxides and one-pot oxidation.
Scheme 7: Thiolysis of epoxides and one-pot oxidation to β-hydroxy sulfoxides using Ga(OTf)3 as a catalyst.
Scheme 8: Ring opening of epoxide using ionic liquids under solvent-free conditions.
Scheme 9: N-Bromosuccinimide-catalyzed ring opening of epoxides.
Scheme 10: LiNTf2-mediated epoxide opening by thiophenol.
Scheme 11: Asymmetric ring-opening of cyclohexene oxide with various thiols catalyzed by zinc L-tartrate.
Scheme 12: Catalytic asymmetric ring opening of symmetrical epoxides with t-BuSH catalyzed by (R)-GaLB (43) wi...
Scheme 13: Asymmetric ring opening of meso-epoxides by p-xylenedithiol catalyzed by a (S,S)-(salen)Cr complex.
Scheme 14: Desymmetrization of meso-epoxide with thiophenol derivatives.
Scheme 15: Enantioselective ring-opening reaction of meso-epoxides with ArSH catalyzed by a C2-symmetric chira...
Scheme 16: Enantioselective ring-opening reaction of stilbene oxides with ArSH catalyzed by a C2-symmetric chi...
Scheme 17: Asymmetric desymmetrization of meso-epoxides using BINOL-based Brønsted acid catalysts.
Scheme 18: Lithium-BINOL-phosphate-catalyzed desymmetrization of meso-epoxides with aromatic thiols.
Scheme 19: Ring-opening reactions of cyclohexene oxide with thiols by using CPs 1-Eu and 2-Tb.
Scheme 20: CBS-oxazaborolidine-catalyzed borane reduction of β-keto sulfides.
Scheme 21: Preparation of β-hydroxy sulfides via connectivity.
Scheme 22: Baker’s yeast-catalyzed reduction of sulfenylated β-ketoesters.
Scheme 23: Sodium-mediated ring opening of epoxides.
Scheme 24: Disulfide bond cleavage-epoxide opening assisted by tetrathiomolybdate.
Scheme 25: Proposed reaction mechanism of disulfide bond cleavage-epoxide opening assisted by tetrathiomolybda...
Scheme 26: Cyclodextrin-catalyzed difunctionalization of alkenes.
Scheme 27: Zinc-catalyzed synthesis of β-hydroxy sulfides from disulfides and alkenes.
Scheme 28: tert-Butyl hydroperoxide-catalyzed hydroxysulfurization of alkenes.
Scheme 29: Proposed mechanism of the radical hydroxysulfurization.
Scheme 30: Rongalite-mediated synthesis of β-hydroxy sulfides from styrenes and disulfides.
Scheme 31: Proposed mechanism of Rongalite-mediated synthesis of β-hydroxy sulfides from styrenes and disulfid...
Scheme 32: Copper(II)-catalyzed synthesis of β-hydroxy sulfides 15e,f from alkenes and basic disulfides.
Scheme 33: CuI-catalyzed acetoxysulfenylation of alkenes.
Scheme 34: CuI-catalyzed acetoxysulfenylation reaction mechanism.
Scheme 35: One-pot oxidative 1,2-acetoxysulfenylation of Baylis–Hillman products.
Scheme 36: Proposed mechanism for the oxidative 1,2-acetoxysulfination of Baylis–Hillman products.
Scheme 37: 1,2-Acetoxysulfenylation of alkenes using DIB/KI.
Scheme 38: Proposed reaction mechanism of the diacetoxyiodobenzene (DIB) and KI-mediated 1,2-acetoxysulfenylat...
Scheme 39: Catalytic asymmetric thiofunctionalization of unactivated alkenes.
Scheme 40: Proposed catalytic cycle for asymmetric sulfenofunctionalization.
Scheme 41: Synthesis of thiosugars using intramolecular thiol-ene reaction.
Scheme 42: Synthesis of leukotriene C-1 by Corey et al.: (a) N-(trifluoroacetyl)glutathione dimethyl ester (3 ...
Scheme 43: Synthesis of pteriatoxins with epoxide thiolysis to attain β-hydroxy sulfides. Reagents: (a) (1) K2...
Scheme 44: Synthesis of peptides containing a β-hydroxy sulfide moiety.
Scheme 45: Synthesis of diltiazem (12) using biocatalytic resolution of an epoxide followed by thiolysis.
Beilstein J. Org. Chem. 2018, 14, 796–802, doi:10.3762/bjoc.14.67
Graphical Abstract
Scheme 1: Reactions of substituted allenes with HVI reagents.
Scheme 2: Chlorination of p-tolylallene (2a) with (dichloroiodo)benzene (1a).
Scheme 3: Chlorination of various aryl-substituted allenes. General conditions: Allene 2a (0.2 mmol, 1 equiv)...
Scheme 4: Chlorination of various α-substituted phenylallene derivatives. General conditions: Allene 2a (0.2 ...
Scheme 5: Chlorination of methoxy-substituted α-methyl phenylallenes. General conditions: Allene 2a (0.2 mmol...
Scheme 6: Control reactions: (a) chlorination of deuterated biphenylallene [D2]-2b; (b) reaction with TEMPO.
Figure 1: Proposed reaction mechanism.
Beilstein J. Org. Chem. 2018, 14, 345–353, doi:10.3762/bjoc.14.22
Graphical Abstract
Scheme 1: One-pot preparation of 4-aryl-3-bromocoumarins 3 from 3-aryl-2-propynoic acids 1 with diphenyliodon...
Scheme 2: One-pot preparation of 3-bromo-4-phenylcoumarins 3a from 3-phenyl-2-propynoic acid (1a) with daryli...
Scheme 3: Derivatization of 3-bromo-4-phenylcoumarin.
Figure 1: ORTEP of 3-bromo-7-chloro-4-phenylcoumarin (3Da).
Scheme 4: Possible reaction pathway.
Beilstein J. Org. Chem. 2017, 13, 2800–2818, doi:10.3762/bjoc.13.273
Graphical Abstract
Scheme 1: Trifluoromethylation of silyl enol ethers.
Scheme 2: Continuous flow trifluoromethylation of ketones under photoredox catalysis.
Scheme 3: Trifluoromethylation of enol acetates.
Scheme 4: Photoredox-catalysed tandem trifluoromethylation/cyclisation of N-arylacrylamides: a route to trifl...
Scheme 5: Tandem trifluoromethylation/cyclisation of N-arylacrylamides using BiOBr nanosheets catalysis.
Scheme 6: Photoredox-catalysed trifluoromethylation/desulfonylation/cyclisation of N-tosyl acrylamides (bpy: ...
Scheme 7: Photoredox-catalysed trifluoromethylation/aryl migration/desulfonylation of N-aryl-N-tosylacrylamid...
Scheme 8: Proposed mechanism for the trifluoromethylation/aryl migration/desulfonylation (/cyclisation) of N-...
Scheme 9: Photoredox-catalysed trifluoromethylation/cyclisation of N-methacryloyl-N-methylbenzamide derivativ...
Scheme 10: Photoredox-catalysed trifluoromethylation/cyclisation of N-methylacryloyl-N-methylbenzamide derivat...
Scheme 11: Photoredox-catalysed trifluoromethylation/dearomatising spirocyclisation of a N-benzylacrylamide de...
Scheme 12: Photoredox-catalysed trifluoromethylation/cyclisation of an unactivated alkene.
Scheme 13: Asymmetric radical aminotrifluoromethylation of N-alkenylurea derivatives using a dual CuBr/chiral ...
Scheme 14: Aminotrifluoromethylation of an N-alkenylurea derivative using a dual CuBr/phosphoric acid catalyti...
Scheme 15: 1,2-Formyl- and 1,2-cyanotrifluoromethylation of alkenes under photoredox catalysis.
Scheme 16: First simultaneous introduction of the CF3 moiety and a Cl atom onto alkenes.
Scheme 17: Chlorotrifluoromethylaltion of terminal, 1,1- and 1,2-substituted alkenes.
Scheme 18: Chorotrifluoromethylation of electron-deficient alkenes (DCE = dichloroethane).
Scheme 19: Cascade trifluoromethylation/cyclisation/chlorination of N-allyl-N-(benzyloxy)methacrylamide.
Scheme 20: Cascade trifluoromethylation/cyclisation (/chlorination) of diethyl 2-allyl-2-(3-methylbut-2-en-1-y...
Scheme 21: Trifluoromethylchlorosulfonylation of allylbenzene derivatives and aliphatic alkenes.
Scheme 22: Access to β-hydroxysulfones from CF3-containing sulfonyl chlorides through a photocatalytic sequenc...
Scheme 23: Cascade trifluoromethylchlorosulfonylation/cyclisation reaction of alkenols: a route to trifluorome...
Scheme 24: First direct C–H trifluoromethylation of arenes and proposed mechanism.
Scheme 25: Direct C–H trifluoromethylation of five- and six-membered (hetero)arenes under photoredox catalysis....
Scheme 26: Alternative pathway for the C–H trifluoromethylation of (hetero)arenes under photoredox catalysis.
Scheme 27: Direct C–H trifluoromethylation of five- and six-membered ring (hetero)arenes using heterogeneous c...
Scheme 28: Trifluoromethylation of terminal olefins.
Scheme 29: Trifluoromethylation of enamides.
Scheme 30: (E)-Selective trifluoromethylation of β-nitroalkenes under photoredox catalysis.
Scheme 31: Photoredox-catalysed trifluoromethylation/cyclisation of an o-azidoarylalkynes.
Scheme 32: Regio- and stereoselective chlorotrifluoromethylation of alkynes.
Scheme 33: PMe3-mediated trifluoromethylsulfenylation by in situ generation of CF3SCl.
Scheme 34: (EtO)2P(O)H-mediated trifluoromethylsulfenylation of (hetero)arenes and thiols.
Scheme 35: PPh3/NaI-mediated trifluoromethylsulfenylation of indole derivatives.
Scheme 36: PPh3/n-Bu4NI mediated trifluoromethylsulfenylation of thiophenol derivatives.
Scheme 37: PPh3/Et3N mediated trifluoromethylsulfinylation of benzylamine.
Scheme 38: PCy3-mediated trifluoromethylsulfinylation of azaarenes, amines and phenols.
Scheme 39: Mono- and dichlorination of carbon acids.
Scheme 40: Monochlorination of (N-aryl-N-hydroxy)acylacetamides.
Scheme 41: Examples of the synthesis of heterocycles fused with β-lactams through a chlorination/cyclisation p...
Scheme 42: Enantioselective chlorination of β-ketoesters and oxindoles.
Scheme 43: Enantioselective chlorination of 3-acyloxazolidin-2-one derivatives (NMM = N-methylmorpholine).
Beilstein J. Org. Chem. 2016, 12, 2570–2576, doi:10.3762/bjoc.12.252
Graphical Abstract
Scheme 1: Syntheses of the HCPs 3 and 5 via thiol–yne reaction.
Figure 1: IR-spectra of tetrathiol 2 (blue), tetraalkyne 1 (red) and HCP 3 (black).
Figure 2: IR-spectra of tetrathiol 2 (blue), hexaalkyne 4 (red) and HCP 3 (black).
Figure 3: SEM images of HCP 3 (left) and HCP 5 (right).
Figure 4: Adsorption isotherms of HCP 3 (green) and HCP 5 (blue) with nitrogen at 77 K. Desorption isotherms ...
Beilstein J. Org. Chem. 2016, 12, 1250–1268, doi:10.3762/bjoc.12.120
Graphical Abstract
Figure 1: Schematic of RiPP biosynthesis. Thiazole/oxazole formation is represented by the blue heterocycle (...
Figure 2: Examples of heterocycles in RiPPs alongside the precursor peptides that these molecules derive from...
Figure 3: Formation of thiazoles and oxazoles in RiPPs. A) Biosynthesis of microcin B17. B) Mechanistic model...
Figure 4: Lanthionine bond formation. A) Nisin and its precursor peptide. B) Mechanism of lanthionine bond fo...
Figure 5: S-[(Z)-2-Aminovinyl]-D-cysteine (AviCys) formation in the epidermin pathway. A) Mechanisms for deca...
Figure 6: Cyclisation in the biosynthesis of thiopeptides. A) Mechanism of TclM-catalysed heterocyclisation i...
Figure 7: ATP-dependent macrocyclisation. A) General mechanism for ATP-dependent macrolactonisation or macrol...
Figure 8: Peptidase-like macrolactam formation. A) General mechanism. B) Examples of RiPPs cyclised by serine...
Figure 9: Structure of autoinducing peptide AIP-I from Staphylococcus aureus and the sequence of the correspo...
Figure 10: Radical cyclisation in RiPP biosynthesis. A) AlbA-catalysed formation of thioethers in the biosynth...
Figure 11: RiPPs with uncharacterised mechanisms of cyclisation. Unusual heterocycles in ComX and methanobacti...
Beilstein J. Org. Chem. 2016, 12, 1153–1169, doi:10.3762/bjoc.12.111
Graphical Abstract
Scheme 1: Synthesis of 2-oxindoles via oxidative processes.
Figure 1: Substrates scope of one-pot ‘transition-metal-free’ IDC. The syntheses of compounds 4a–s according ...
Figure 2: Further substrates scope of one-pot ‘transition metal-free’ IDC. Conditions A: KOt-Bu, iodine; cond...
Figure 3: Substrates scope of ‘transition-metal-free’ IDC using KOt-Bu/I2. Reproduced from [46].
Figure 4: C-Alkylation of anilides using KOt-Bu.
Figure 5: Substrates scope of ‘transition-metal-free’ IDC of C-alkylated anilides using DBU/I2.
Scheme 2: Oxidative coupling of C-arylated anilides (±)-11a–d. The synthesis of 12b as per method A has been ...
Scheme 3: Synthesis of spirocyclic product through IDC The synthesis of 14 as per method A has been reproduce...
Scheme 4: Dimerization of β-N-aryl-amidoesters 3a and b. Reproduced from [46].
Scheme 5: Synthesis of dimeric 2-oxindoles utilizing IDC. The syntheses of 19a and b have been reproduced fro...
Scheme 6: Plausible mechanism of ‘transition-metal-free’ IDC The mechanistic consideration in Scheme 6 has been repro...
Scheme 7: Intramolecular-dehydrogenative-coupling (IDC) of 3a and 5a. Reproduced from [46].
Scheme 8: IDC of 3a and 5a using different oxidants. Reproduced from [46].
Scheme 9: Synthesis of 3-substituted-2-oxindoles from benzyl esters.
Scheme 10: 3-Substituted-2-oxindoles from p-methoxybenzyl esters.
Scheme 11: Synthetic elaboration using Tsuji–Trost reactions. Reproduced from [46].
Beilstein J. Org. Chem. 2015, 11, 2654–2660, doi:10.3762/bjoc.11.285
Graphical Abstract
Figure 1: Structure of PGI2 and beraprost (1).
Scheme 1: Retrosynthetic analysis of beraprost (1).
Scheme 2: Preparation of Michael precursors 7 and 8.
Scheme 3: First attempt at the synthesis of 2 from 6.
Scheme 4: Achievement of a formal synthesis of 2.
Beilstein J. Org. Chem. 2015, 11, 1008–1016, doi:10.3762/bjoc.11.113
Graphical Abstract
Figure 1: Natural products and drugs featuring imide core.
Scheme 1: Attempted methodology and its outcome (reaction conditions: (a) Pd(OAc)2 (10 mol %), ammonium persu...
Scheme 2: A practical synthesis of vernakalant (11).
Figure 2: Radical trapping experiment.
Beilstein J. Org. Chem. 2015, 11, 66–73, doi:10.3762/bjoc.11.10
Graphical Abstract
Scheme 1: Nucleophilic radical addition to imines mediated by titanium salts.
Scheme 2: Radical domino approach to the synthesis of β-aminoacohols triggered by titanium salts.
Scheme 3: Competitive imine formation from THF.
Scheme 4: Reaction mechanism.
Scheme 5: Domino reaction in the presence of ethanol.
Beilstein J. Org. Chem. 2014, 10, 2930–2954, doi:10.3762/bjoc.10.312
Graphical Abstract
Scheme 1: The Grignard-based synthesis of 6-alkyl phenanthridine.
Scheme 2: Radical-mediated synthesis of 6-arylphenanthridine [14].
Scheme 3: A t-BuO• radical-assisted homolytic aromatic substitution mechanism proposed for the conversion of ...
Scheme 4: Synthesis of 5,6-unsubstituted phenanthridine starting from 2-iodobenzyl chloride and aniline [17].
Scheme 5: Phenanthridine synthesis initiated by UV-light irradiation photolysis of acetophenone O-ethoxycarbo...
Scheme 6: PhI(OAc)2-mediated oxidative cyclization of 2-isocyanobiphenyls with CF3SiMe3 [19,20].
Scheme 7: Targeting 6-perfluoroalkylphenanthridines [21,22].
Scheme 8: Easily accessible biphenyl isocyanides reacting under mild conditions (room temp., visible light ir...
Scheme 9: Microwave irradiation of Diels–Alder adduct followed by UV irradiation of dihydrophenanthridines yi...
Scheme 10: A representative palladium catalytic cycle.
Scheme 11: The common Pd-catalyst for the biphenyl conjugation results simultaneously in picolinamide-directed...
Scheme 12: Pd(0)-mediated cyclisation of imidoyl-selenides forming 6-arylphenanthridine derivatives [16]. The inse...
Scheme 13: Palladium-catalysed phenanthridine synthesis.
Scheme 14: Aerobic domino Suzuki coupling combined with Michael addition reaction in the presence of a Pd(OAc)2...
Scheme 15: Rhodium-catalysed alkyne [2 + 2 + 2] cycloaddition reactions [36].
Scheme 16: The O-acetyloximes derived from 2′-arylacetophenones underwent N–O bond cleavage and intramolecular ...
Scheme 17: C–H arylation with aryl chloride in the presence of a simple diol complex with KOt-Bu (top) [39]; for s...
Scheme 18: The subsequent aza-Claisen rearrangement, ring-closing enyne metathesis and Diels–Alder reaction – ...
Scheme 19: Phenanthridine central-ring cyclisation with simultaneous radical-driven phosphorylation [42].
Scheme 20: Three component reaction yielding the benzo[a]phenanthridine core in excellent yields [44].
Scheme 21: a) Reaction of malononitrile and 1,3-indandione with BEP to form the cyclised DPP products; b) pH c...
Figure 1: Schematic presentation of the intercalative binding mode by the neighbour exclusion principle and i...
Figure 2: Urea and guanidine derivatives of EB with modified DNA interactions [57].
Figure 3: Structure of mono- (3) and bis-biguanide (4) derivative. Fluorescence (y-axis normalised to startin...
Scheme 22: Bis-phenanthridinium derivatives (5–7; inert aliphatic linkers, R = –(CH2)4– or –(CH2)6–): rigidity...
Figure 4: Series of amino acid–phenanthridine building blocks (general structure 10; R = H; Gly) and peptide-...
Figure 5: General structure of 45 bis-ethidium bromide analogues. Reproduced with permission from [69]. Copyright...
Scheme 23: Top: Recognition of poly(U) by 12 and ds-polyAH+ by 13; bottom: Recognition of poly(dA)–poly(dT) by ...
Figure 6: The bis-phenanthridinium–adenine derivative 15 (LEFT) showed selectivity towards complementary UMP;...
Figure 7: The neomycin–methidium conjugate targeting DNA:RNA hybrid structures [80].
Figure 8: Two-colour RNA intercalating probe for cell imaging applications: Left: Chemical structure of EB-fl...
Figure 9: The ethidium bromide nucleosides 17 (top) and 18 (bottom). DNA duplex set 1 and 2 (E = phenanthridi...
Figure 10: Left: various DNA duplexes; DNA1 and DNA2 used to study the impact on the adjacent basepair type on...
Figure 11: Structure of 4,9-DAP derivative 19; Rright: MIAPaCa-2 cells stained with 10 μM 19 after 60 and 120 ...
Figure 12: Examples of naturally occurring phenanthridine analogues.
Beilstein J. Org. Chem. 2014, 10, 1488–1494, doi:10.3762/bjoc.10.153
Graphical Abstract
Figure 1: Repeating unit of the A-band polysaccharide of P. aeruginosa.
Scheme 1: Preparation of the monomeric building blocks; reagents and conditions: i) Pyr., BzCl, 0 °C–rt; ii) ...
Figure 2: Retrosynthetic analysis.
Scheme 2: Sequential stepwise synthesis of the trisaccharide; reagents and conditions: i) TMSOTf, DCM, molecu...
Scheme 3: Synthesis of the trisaccharide by sequential one-pot glycosylation reactions; reagents and conditio...
Scheme 4: Synthesis of the target trisaccharide via global deoxygenation strategy; reagents and conditions: i...
Beilstein J. Org. Chem. 2014, 10, 1272–1281, doi:10.3762/bjoc.10.128
Graphical Abstract
Figure 1: Selected examples of endoperoxide-containing natural products.
Scheme 1: Endoperoxide formation via cation radicals. In both examples, single electron oxidation is followed...
Scheme 2: Diversification strategy for endoperoxide synthesis by single electron transfer. E*red vs SCE [20].
Figure 2: ORTEP of 3a.
Scheme 3: Proposed mechanism for endoperoxide synthesis from tethered dienes.
Scheme 4: Competing formal [3,3] pathway.
Beilstein J. Org. Chem. 2014, 10, 863–876, doi:10.3762/bjoc.10.83
Graphical Abstract
Scheme 1: Examples of photoinitiating systems.
Figure 1: Previously reported PIC (based on metal complexes) [45-52].
Figure 2: Previously reported PIC (metal free organic molecules) [54,55].
Scheme 2: Reaction mechanisms for the three-component system PIC/eA/E-Z.
Scheme 3: Reaction mechanisms for the two-component system PIC/eA.
Scheme 4: Reaction mechanisms for the system PIC/eA/add.
Scheme 5: Reaction mechanisms for the system PIC/eD/B-Y.
Figure 3: Typical oxidation and reduction agents used through the photoredox catalysis approach in polymeriza...
Figure 4: Typical monomers that can be polymerized through a photoredox catalysis approach.
Scheme 6: Reaction mechanisms for the system Ru(bpy)32+/Ph2I+/R3SiH.
Scheme 7: Reaction mechanisms for the Ru(ligand)32+/Ph3S+/R3SiH system.
Scheme 8: Reaction mechanisms for the Ru(ligand)32+/Ph2I+/NVK system upon visible lights.
Scheme 9: Reaction mechanisms for the violanthrone/Ph2I+/TTMSS (R3SiH) system upon red lights.
Scheme 10: Reaction mechanisms for the Tr-AD/R-Br/MDEA system upon visible lights.
Scheme 11: The photoredox catalysis for controlled polymerization reactions.
Scheme 12: Reaction mechanisms for the Ru(ligand)32+/MDEA/R-Br system upon visible lights.
Scheme 13: Reaction mechanisms for the Violanthrone/Ru(ligand)32+/Ph2I+/R3SiH system upon visible lights.
Scheme 14: Reaction mechanisms for the MK/amine/triazine system upon visible lights.
Figure 5: The new proposed PIC (Ir(piq)2(tmd)).
Figure 6: UV–visible light absorption spectra for Ir(piq)2(tmd) (2) and Ir(ppy)3 (1); solvent: acetonitrile.
Figure 7: (A) cyclic voltamogramm for Ir(piq)2(tmd) in acetonitrile; (B) absorption (a) and luminescence (b) ...
Figure 8: Photolysis of a Ir(piq)2(tmd)/Ph2I+ solution ([Ph2I+] = 0.023 M, in acetonitrile) upon a halogen la...
Figure 9: ESR spin-trapping spectra for the irradiation of a Ir(piq)2(tmd)/Ph2I+ solution in the presence of ...
Figure 10: (A) Photopolymerization profile of EPOX; photoinitiating system: Ir(piq)2(tmd)/Ph2I+/NVK (1%/2%/3%)...
Figure 11: (A) Photopolymerization profile of TMPTA; initiating systems: (1) Ir(piq)2(tmd)/MDEA (1%/2%) and (2...
Beilstein J. Org. Chem. 2013, 9, 1907–1916, doi:10.3762/bjoc.9.225
Graphical Abstract
Scheme 1: Generation of NO3• (a) in the atmosphere, (b) under experimental conditions.
Figure 1: Polyester-model systems studied in this work.
Scheme 2: Products of the reaction of polyester model compounds 1–3 with NO3• in the absence of other radical...
Scheme 3: Proposed mechanism for the reaction of m-toluic acid neopentyl ester (3) with NO3• in the absence o...
Scheme 4: Products of the reaction of polyester-model compounds 1–3 with NO3• in presence of NO2•, O3, and O2....
Scheme 5: Proposed mechanism for the reaction of m-toluic acid neopentyl ester (3) with NO3• in presence of NO...
Beilstein J. Org. Chem. 2013, 9, 1083–1092, doi:10.3762/bjoc.9.120
Graphical Abstract
Figure 1: O-Ethoxycarbonyl oximes prepared.
Scheme 1: Photochemical reactions of biphenyl oxime carbonates.
Figure 2: EPR spectrum during photolysis of 1f in t-BuPh at 240 K. Top (black): experimental spectrum. Bottom...
Figure 3: EPR spectrum during photolysis of 2a in t-BuPh at 230 K. Top (blue): experiment; bottom (red): simu...
Scheme 2: Ring closure of iminyl radicals derived from 2a,b.
Figure 4: DFT computed structures for 5a, 11a and their cyclisation transition states (TS). Top line: spin de...
Beilstein J. Org. Chem. 2013, 9, 891–899, doi:10.3762/bjoc.9.102
Graphical Abstract
Scheme 1: Representative phenanthridine compounds and our synthetic strategy based on Pd-catalyzed sequential...
Figure 1: Substrate scope of the Pd-catalyzed PA-directed C–H arylation reaction. All reactions were carried ...
Figure 2: Substrate scope of this phenanthridine synthesis. All reactions were carried out in a 10 mL glass v...