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Search for "perfluoroalkyl sulfides" in Full Text gives 2 result(s) in Beilstein Journal of Organic Chemistry.
Recent advances in transition-metal-catalyzed incorporation of fluorine-containing groups
- Xiaowei Li,
- Xiaolin Shi,
- Xiangqian Li and
- Dayong Shi
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.
Aromatic and heterocyclic perfluoroalkyl sulfides. Methods of preparation
- Vladimir N. Boiko
Beilstein J. Org. Chem. 2010, 6, 880–921, doi:10.3762/bjoc.6.88
- Vladimir N. Boiko Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Murmanskaya St. 5, 02094 Kiev, Ukraine 10.3762/bjoc.6.88 Abstract This review covers all of the common methods for the syntheses of aromatic and heterocyclic perfluoroalkyl sulfides, a class of compounds
- -process; perfluoroalkylation; perfluoroalkyl sulfides; SRF-introduction; Review 1. Introduction Perfluoroalkyl sulfides of aromatic and heterocyclic compounds have been an important aspect in the general development of organofluorine chemistry over the last twenty years. Alkyl aryl sulfides containing
- of the reviews on the subject are very general [28][30][32][36]. The present work reviews synthetic methods employed to prepare aromatic and heterocyclic perfluoroalkyl sulfides and is systematized depending on the mode of constructing the SRF groups and also on the nature of the starting materials
Graphical Abstract
Figure 1: Examples of industrial fluorine-containing bio-active molecules.
Figure 2: CF3(S)- and CF3(O)-containing pharmacologically active compounds.
Figure 3: Hypotensive candidates with SRF and SO2RF groups – analogues of Losartan and Nifedipin.
Figure 4: The variety of the pharmacological activity of RFS-substituted compounds.
Figure 5: Recent examples of compounds containing RFS(O)n-groups [12-18].
Scheme 1: Fluorination of ArSCCl3 to corresponding ArSCF3 derivatives. For references see: a[38-43]; b[41,42]; c[43]; d[44]; e[38-43,45-47]; f[38-43,48,49]; g...
Scheme 2: Preparation of aryl pentafluoroethyl sulfides.
Scheme 3: Mild fluorination of the aryl SCF2Br derivatives.
Scheme 4: HF fluorinations of aryl α,α,β-trichloroisobutyl sulfide at various conditions.
Scheme 5: Monofluorination of α,α-dichloromethylene group.
Scheme 6: Electrophilic substitution of phenols with CF3SCl [69].
Scheme 7: Introduction of SCF3 groups into activated phenols [71-74].
Scheme 8: Preparation of tetrakis(SCF3)-4-methoxyphenol [72].
Scheme 9: The interactions of resorcinol and phloroglucinol derivatives with RFSCl.
Scheme 10: Reactions of anilines with CF3SCl.
Scheme 11: Trifluoromethylsulfanylation of anilines with electron-donating groups in the meta position [74].
Scheme 12: Reaction of benzene with CF3SCl/CF3SO3H [77].
Scheme 13: Reactions of trifluoromethyl sulfenyl chloride with aryl magnesium and -mercury substrates.
Scheme 14: Reactions of pyrroles with CF3SCl.
Scheme 15: Trifluoromethylsulfanylation of indole and indolizines.
Scheme 16: Reactions of N-methylpyrrole with CF3SCl [80,82].
Scheme 17: Reactions of furan, thiophene and selenophene with CF3SCl.
Scheme 18: Trifluoromethylsulfanylation of imidazole and thiazole derivatives [83].
Scheme 19: Trifluoromethylsulfanylation of pyridine requires initial hydride reduction.
Scheme 20: Introduction of additional RFS-groups into heterocyclic compounds in the presence of CF3SO3H.
Scheme 21: Introduction of additional RFS-groups into pyrroles [82,87].
Scheme 22: By-products in reactions of pyrroles with CF3SCl [82].
Scheme 23: Reaction of aromatic iodides with CuSCF3 [93,95].
Scheme 24: Reaction of aromatic iodides with RFZCu (Z = S, Se), RF = CF3, C6F5 [93,95,96].
Scheme 25: Side reactions during trifluoromethylsulfanylation of aromatic iodides with CF3SCu [98].
Scheme 26: Reactions with in situ generated CuSCF3.
Scheme 27: Perfluoroalkylthiolation of aryl iodides with bulky RFSCu [105].
Scheme 28: In situ formation and reaction of RFZCu with aryl iodides.
Figure 6: Examples of compounds obtained using in situ generated RFZCu methodology [94].
Scheme 29: Introduction of SCF3 group into aromatics via difluorocarbene.
Scheme 30: Tetrakis(dimethylamino)ethylene dication trifluoromethyl thiolate as a stable reagent for substitut...
Scheme 31: The use of CF2=S/CsF or (CF3S)2C=S/CsF for the introduction of CF3S groups into fluorinated heteroc...
Scheme 32: One-pot synthesis of ArSCF3 from ArX, CCl2=S and KF.
Scheme 33: Reaction of aromatics with CF3S− Kat+ [115].
Scheme 34: Reactions of activated aromatic chlorides with AgSCF3/KI.
Scheme 35: Comparative CuSCF3/KI and Hg(SCF3)2/KI reactions.
Scheme 36: Me3SnTeCF3 – a reagent for the introduction of the TeCF3 group.
Scheme 37: Sandmeyer reactions with CuSCF3.
Scheme 38: Reactions of perfluoroalkyl iodides with alkali and organolithium reagents.
Scheme 39: Perfluoroalkylation with preliminary breaking of the disulfide bond.
Scheme 40: Preparation of RFS-substituted anilines from dinitrodiphenyl disulfides.
Scheme 41: Photochemical trifluoromethylation of 2,4,6-trimercaptochlorobenzene [163].
Scheme 42: Putative process for the formation of B, C and D.
Scheme 43: Trifluoromethylation of 2-mercapto-4-hydroxy-6-trifluoromethylyrimidine [145].
Scheme 44: Deactivation of 2-mercapto-4-hydroxypyrimidines S-centered radicals.
Scheme 45: Perfluoroalkylation of thiolates with CF3Br under UV irradiation.
Scheme 46: Catalytic effect of methylviologen for RF• generation.
Scheme 47: SO2−• catalyzed trifluoromethylation.
Scheme 48: Electrochemical reduction of CF3Br in the presence of SO2 [199,200].
Scheme 49: Participation of SO2 in the oxidation of ArSCF3−•.
Scheme 50: Electron transfer cascade involving SO2 and MV.
Scheme 51: Four stages of the SRN1 mechanism for thiol perfluoroalkylation.
Scheme 52: A double role of MV in the catalysis of RFI reactions with aryl thiols.
Scheme 53: Photochemical reaction of pentafluoroiodobenzene with trifluoromethyl disulfide.
Scheme 54: N- Trifluoromethyl-N-nitrosobenzene sulfonamide – a source of CF3• radicals [212,213].
Scheme 55: Radical trifluoromethylation of organic disulfides with ArSO2N=NCF3.
Scheme 56: Barton’s S-perfluoroalkylation reactions [216].
Scheme 57: Decarboxylation of thiohydroxamic esters in the presence of C6F13I.
Scheme 58: Reactions of thioesters of trifluoroacetic and trifluoromethanesulfonic acids in the presence of ar...
Scheme 59: Perfluoroalkylation of polychloropyridine thiols with xenon perfluorocarboxylates or XeF2 [222,223].
Scheme 60: Interaction of Xe(OCORF)2 with nitroaryl disulfide [227].
Scheme 61: Bi(CF3)3/Cu(OCOCH3)2 trifluoromethylation of thiophenolate [230].
Scheme 62: Reaction of fluorinated carbanions with aryl sulfenyl chlorides.
Scheme 63: Reaction of methyl perfluoromethacrylate with PhSCl in the presence of fluoride.
Scheme 64: Reactions of ArSCN with potassium and magnesium perfluorocarbanions [237].
Scheme 65: Reactions of RFI with TDAE and organic disulfides [239,240].
Scheme 66: Decarboxylation of perfluorocarboxylates in the presence of disulfides [245].
Scheme 67: Organization of a stable form of “CF3−” anion in the DMF.
Scheme 68: Silylated amines in the presence of fluoride can deprotonate fluoroform for reaction with disulfide...
Figure 7: Other examples of aminomethanols [264].
Scheme 69: Trifluoromethylation of diphenyl disulfide with PhSO2CF3/t-BuOK.
Scheme 70: Amides of trifluoromethane sulfinic acid are sources of CF3− anion.
Scheme 71: Trifluoromethylation of various thiols using “hyper-valent” iodine (III) reagent [279].
Scheme 72: Trifluoromethylation of p-nitrothiophenolate with diaryl CF3 sulfonium salts [280].
Scheme 73: Trifluoromethyl transfer from dibenzo (CF3)S-, (CF3)Se- and (CF3)Te-phenium salts to thiolates [283].
Scheme 74: Multi-stage paths for synthesis of dibenzo-CF3-thiophenium salts [61].
