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Search for "dithiocarbamates" in Full Text gives 11 result(s) in Beilstein Journal of Organic Chemistry.
Synthetic reactions driven by electron-donor–acceptor (EDA) complexes
- Zhonglie Yang,
- Yutong Liu,
- Kun Cao,
- Xiaobin Zhang,
- Hezhong Jiang and
- Jiahong Li
Beilstein J. Org. Chem. 2021, 17, 771–799, doi:10.3762/bjoc.17.67
- successfully applied to the gram scale, providing a step towards assorted aryl sulfide structural units with medicinal value. In 2019, Yang and colleagues [52] developed a method for preparing S-aryl dithiocarbamates 135 by a multicomponent reaction of an EDA complex under visible-light irradiation (Scheme 47
- ). A number of aryl halides reacted smoothly, providing moderate to good yields for analogous S-aryl dithiocarbamates. To further demonstrate the synthetic application of this protocol, a gram scale of 135 has been tested, giving a yield of 72%. By constructing C–N- and C–S bonds simultaneously in one
Graphical Abstract
Scheme 1: The electron transfer process in EDA complexes.
Scheme 2: Synthesis of benzo[b]phosphorus oxide 3 initiated by an EDA complex.
Scheme 3: Mechanism of the synthesis of quinoxaline derivative 7.
Scheme 4: Synthesis of imidazole derivative 10 initiated by an EDA complex.
Scheme 5: Synthesis of sulfamoylation product 12 initiated by an EDA complex.
Scheme 6: Mechanism of the synthesis of sulfamoylation product 12.
Scheme 7: Synthesis of indole derivative 22 initiated by an EDA complex.
Scheme 8: Synthesis of perfluoroalkylated pyrimidines 26 initiated by an EDA complex.
Scheme 9: Synthesis of phenanthridine derivative 29 initiated by an EDA complex.
Scheme 10: Synthesis of cis-tetrahydroquinoline derivative 32 initiated by an EDA complex.
Scheme 11: Mechanism of the synthesis of cis-tetrahydroquinoline derivative 32.
Scheme 12: Synthesis of phenanthridine derivative 38 initiated by an EDA complex.
Scheme 13: Synthesis of spiropyrroline derivative 40 initiated by an EDA complex.
Scheme 14: Synthesis of benzothiazole derivative 43 initiated by an EDA complex.
Scheme 15: Synthesis of perfluoroalkyl-s-triazine derivative 45 initiated by an EDA complex.
Scheme 16: Synthesis of indoline derivative 47 initiated by an EDA complex.
Scheme 17: Mechanism of the synthesis of spirocyclic indoline derivative 47.
Scheme 18: Synthesis of cyclobutane product 50 initiated by an EDA complex.
Scheme 19: Mechanism of the synthesis of spirocyclic indoline derivative 50.
Scheme 20: Synthesis of 1,3-oxazolidine compound 59 initiated by an EDA complex.
Scheme 21: Synthesis of trifluoromethylated product 61 initiated by an EDA complex.
Scheme 22: Synthesis of indole alkylation product 64 initiated by an EDA complex.
Scheme 23: Synthesis of perfluoroalkylation product 67 initiated by an EDA complex.
Scheme 24: Synthesis of hydrotrifluoromethylated product 70 initiated by an EDA complex.
Scheme 25: Synthesis of β-trifluoromethylated alkyne product 71 initiated by an EDA complex.
Scheme 26: Mechanism of the synthesis of 2-phenylthiophene derivative 74.
Scheme 27: Synthesis of allylated product 80 initiated by an EDA complex.
Scheme 28: Synthesis of trifluoromethyl-substituted alkynyl product 84 initiated by an EDA complex.
Scheme 29: Synthesis of dearomatized fluoroalkylation product 86 initiated by an EDA complex.
Scheme 30: Mechanism of the synthesis of dearomatized fluoroalkylation product 86.
Scheme 31: Synthesis of C(sp3)–H allylation product 91 initiated by an EDA complex.
Scheme 32: Synthesis of perfluoroalkylation product 93 initiated by an EDA complex.
Scheme 33: Synthesis of spirocyclic indolene derivative 95 initiated by an EDA complex.
Scheme 34: Synthesis of perfluoroalkylation product 97 initiated by an EDA complex.
Scheme 35: Synthesis of alkylated indole derivative 100 initiated by an EDA complex.
Scheme 36: Mechanism of the synthesis of alkylated indole derivative 100.
Scheme 37: Synthesis of arylated oxidized indole derivative 108 initiated by an EDA complex.
Scheme 38: Synthesis of 4-ketoaldehyde derivative 111 initiated by an EDA complex.
Scheme 39: Mechanism of the synthesis of 4-ketoaldehyde derivative 111.
Scheme 40: Synthesis of perfluoroalkylated olefin 118 initiated by an EDA complex.
Scheme 41: Synthesis of alkylation product 121 initiated by an EDA complex.
Scheme 42: Synthesis of acylation product 123 initiated by an EDA complex.
Scheme 43: Mechanism of the synthesis of acylation product 123.
Scheme 44: Synthesis of trifluoromethylation product 126 initiated by an EDA complex.
Scheme 45: Synthesis of unnatural α-amino acid 129 initiated by an EDA complex.
Scheme 46: Synthesis of thioether derivative 132 initiated by an EDA complex.
Scheme 47: Synthesis of S-aryl dithiocarbamate product 135 initiated by an EDA complex.
Scheme 48: Mechanism of the synthesis of S-aryl dithiocarbamate product 135.
Scheme 49: Synthesis of thioether product 141 initiated by an EDA complex.
Scheme 50: Mechanism of the synthesis of borate product 144.
Scheme 51: Synthesis of boronation product 148 initiated by an EDA complex.
Scheme 52: Synthesis of boration product 151 initiated by an EDA complex.
Scheme 53: Synthesis of boronic acid ester derivative 154 initiated by an EDA complex.
Scheme 54: Synthesis of β-azide product 157 initiated by an EDA complex.
Scheme 55: Decarboxylation reaction initiated by an EDA complex.
Scheme 56: Synthesis of amidated product 162 initiated by an EDA complex.
Scheme 57: Synthesis of diethyl phenylphosphonate 165 initiated by an EDA complex.
Scheme 58: Mechanism of the synthesis of diethyl phenylphosphonate derivative 165.
Scheme 59: Synthesis of (Z)-2-iodovinyl phenyl ether 168 initiated by an EDA complex.
Scheme 60: Mechanism of the synthesis of (Z)-2-iodovinyl phenyl ether derivative 168.
Scheme 61: Dehalogenation reaction initiated by an EDA complex.
Regio- and stereoselective synthesis of new ensembles of diversely functionalized 1,3-thiaselenol-2-ylmethyl selenides by a double rearrangement reaction
- Svetlana V. Amosova,
- Andrey A. Filippov,
- Nataliya A. Makhaeva,
- Alexander I. Albanov and
- Vladimir A. Potapov
Beilstein J. Org. Chem. 2020, 16, 515–523, doi:10.3762/bjoc.16.47
- was developed during the last ten years based on new directions for nucleophilic substitution reactions proceeding via intermediate seleniranium cations 2 generated from thiaselenole 1. We have carried out new regioselective reactions of thiaselenole 1 with dithiocarbamates [31], ketones [37], thiols
Graphical Abstract
Scheme 1: Possible formation of reaction products starting from 1 via seleniranium 2 or thiiranium cations 3.
Scheme 2: Unusual regio- and stereoselective nucleophilic reactions of thiaselenole 1 at two centers of the s...
Scheme 3: Reactions of thiaselenole 1 with С- and S-centered nucleophiles affording new families of linear un...
Scheme 4: The reactions of thiaselenole 1 with the formation of polyfunctionalized 2,3-dihydro-1,4-thiaseleni...
Scheme 5: The synthesis of new 1,3-thiaselenole ensembles by reactions of thiaselenole 1 with mercapto benzaz...
Scheme 6: The formation of product 4 via compound 5 by the reaction of thiaselenole 1 with potassium selenocy...
Figure 1: Monitoring the reaction of thiaselenole 1 with KSeCN by 1H NMR spectroscopy (in accordance with the...
Scheme 7: The reaction pathway for the formation of compounds 4 and 5.
Scheme 8: Synthesis of new ensembles of 1,3-thiaselenol-2-ylmethyl selenides 6a–l (77Se NMR data are included...
Scheme 9: The synthesis of vinyl selenides 7a,b through nucleophilic addition of 1,3-thiaselenol-2-ylmethylse...
Scheme 10: One-pot synthesis of diselenide 8 from thiaselenole 1 (77Se NMR data are included).
Scheme 11: Synthesis of compounds 6a–j from diselenide 8.
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.
A novel three-component reaction between isocyanides, alcohols or thiols and elemental sulfur: a mild, catalyst-free approach towards O-thiocarbamates and dithiocarbamates
- András György Németh,
- György Miklós Keserű and
- Péter Ábrányi-Balogh
Beilstein J. Org. Chem. 2019, 15, 1523–1533, doi:10.3762/bjoc.15.155
- been developed between isocyanides, sulfur and alcohols or thiols under mild reaction conditions to afford O-thiocarbamates and dithiocarbamates in moderate to good yields. The one-pot reaction cascade involves the formation of an isothiocyanate intermediate, thus a catalyst-free synthesis of
- as enzyme inhibitors [26] or antitumor agents [27]. These species are also used as valuable synthetic intermediates [28] and chemosensors for mercury and silver [29][30]. The general methods for the synthesis of O-thiocarbamates and dithiocarbamates traditionally rely on substitution reactions of the
- toxic, malodorous and/or extremely corrosive byproducts generated by the elimination of the halogen atoms. One should note that the application of these halogenated thiocarbonic acid derivatives might be dangerous and require thorough precaution. Considering dithiocarbamates, a number of methods are
Graphical Abstract
Scheme 1: Synthetic routes to O-thiocarbamates and dithiocarbamates.
Scheme 2: Substrate scope of isocyanides. aReaction conditions: 1 (1 mmol), S8 (2 mmol), 2a (2mmol), NaH (2 m...
Scheme 3: Substrate scope of alcohols. Reaction conditions: 1a (1 mmol), S8 (2 mmol), 2 (2mmol), NaH (2 mmol)...
Scheme 4: Substrate scope of thiols. Reaction conditions: 1a (1 mmol), S8 (1.2 mmol), 4 (2 mmol), NaOH (2 mmo...
Scheme 5: Scaled-up synthesis for 3a.
Scheme 6: Multicomponent domino synthesis of quinazolinone 7.
Scheme 7: Control experiments.
Scheme 8: Proposed mechanism.
Atom-economical group-transfer reactions with hypervalent iodine compounds
- Andreas Boelke,
- Peter Finkbeiner and
- Boris J. Nachtsheim
Beilstein J. Org. Chem. 2018, 14, 1263–1280, doi:10.3762/bjoc.14.108
- respective diaryliodonium salts 1. An atom efficient S-arylation of tetraalkylthiuram disulfides 6 was developed by Dong and co-workers under Cu(I)-catalysis (Scheme 5) [28]. This reaction yields two equivalents of S-aryl dithiocarbamates 7 and 7’ in typically high yields applying only one equivalent of a
- diaryliodonium salt 1. It is worth to mention, that the AE of 51% (for Ar1 = Ar2 = Ph, X = TfO–, R = Me) is only valid if both dithiocarbamates 7 and 7’ are defined as desired reaction products. If symmetrical diaryliodonium salts are used, as also demonstrated, only one arylation product is formed. The proposed
- dithiocarbamates 7 and 7’ from one equivalent of diaryliodonium salt 1. Synthesis of substituted isoindolin-1-ones 9 from 2-formylbenzonitrile 8 and the postulated reaction mechanism. Domino C-/N-arylation of indoles 10. Domino modification of N-heterocycles 12 via in situ-generated directing groups. Synthesis of
Graphical Abstract
Scheme 1: Overview of different types of iodane-based group-transfer reactions and their atom economy based o...
Scheme 2: (a) Structure of diaryliodonium salts 1. (b) Diarylation of a suitable substrate A with one equival...
Scheme 3: Synthesis of biphenyls 3 and 3’ with symmetrical diaryliodonium salts 1.
Scheme 4: Synthesis of diaryl thioethers 5.
Scheme 5: Synthesis of two distinct S-aryl dithiocarbamates 7 and 7’ from one equivalent of diaryliodonium sa...
Scheme 6: Synthesis of substituted isoindolin-1-ones 9 from 2-formylbenzonitrile 8 and the postulated reactio...
Scheme 7: Domino C-/N-arylation of indoles 10.
Scheme 8: Domino modification of N-heterocycles 12 via in situ-generated directing groups.
Scheme 9: Synthesis of triarylamines 17 through a double arylation of anilines.
Scheme 10: Selective conversion of novel aryl(imidazolyl)iodonium salts 1b to 1,5-disubstituted imidazoles 18.
Scheme 11: Selected examples for the application of cyclic diaryliodonium salts 19.
Scheme 12: Tandem oxidation–arylation sequence with (dicarboxyiodo)benzenes 20.
Scheme 13: Oxidative α-arylation via the transfer of an intact 2-iodoaryl group.
Scheme 14: Tandem ortho-iodination/O-arylation cascade with PIDA derivatives 20b.
Scheme 15: Synthesis of meta-N,N-diarylaminophenols 28 and the postulated mechanism.
Scheme 16: (Dicarboxyiodo)benzene-mediated metal-catalysed C–H amination and arylation.
Scheme 17: Postulated mechanism for the amination–arylation sequence.
Scheme 18: Auto-amination and cross-coupling of PIDA derivatives 20c.
Scheme 19: Tandem C(sp3)–H olefination/C(sp2)–H arylation.
Scheme 20: Atom efficient functionalisations with benziodoxolones 36.
Scheme 21: Atom-efficient synthesis of furans 39 from benziodoxolones 36a and their further derivatisations.
Scheme 22: Oxyalkynylation of diazo compounds 42.
Scheme 23: Enantioselective oxyalkynylation of diazo compounds 42’.
Scheme 24: Iron-catalysed oxyazidation of enamides 45.
One-pot three-component route for the synthesis of S-trifluoromethyl dithiocarbamates using Togni’s reagent
- Azim Ziyaei Halimehjani,
- Martin Dračínský and
- Petr Beier
Beilstein J. Org. Chem. 2017, 13, 2502–2508, doi:10.3762/bjoc.13.247
- /bjoc.13.247 Abstract A one-pot three-component route for the synthesis of S-trifluoromethyl dithiocarbamates by the reaction of secondary amines, carbon disulfide and Togni’s reagent is described. The reactions proceed in moderate to good yields. A similar reaction using a primary aliphatic amine
- rotation are in reasonable agreement with the experiments. Keywords: dithiocarbamates; electrophilic trifluoromethylation; Togni reagents; Introduction Dithiocarbamates are well known for their manifold applications as pesticides, fungicides and crop protection agents in agriculture [1][2][3], as
- dithiocarbamates via a one-pot reaction of an amine, CS2 and an electrophile is of great interest due to its simplicity and environmental friendly procedure. Diverse electrophiles including alkyl halides [18], epoxides [19], alkenes [20][21][22], aldehydes [23], and alcohols [24] were applied for the synthesis of
Graphical Abstract
Scheme 1: Synthetic routes for the preparation of trifluoromethyl dithiocarbamates.
Scheme 2: Synthesis of S-trifluoromethyl dithiocarbamates. Isolated yields are given in parentheses.
Scheme 3: Formation of benzyl isothiocyanate in a reaction with benzylamine.
Figure 1: Variable temperature 1H NMR spectra of compound 4c (CH2 region on the left and CH3 region on the ri...
Figure 2: The Eyring plot obtained for the rotation around the N–C bond in compound 4c.
Figure 3: The optimized structure of compound 4b (left) and the transition state structure for the rotation a...
Strategies toward protecting group-free glycosylation through selective activation of the anomeric center
- A. Michael Downey and
- Michal Hocek
Beilstein J. Org. Chem. 2017, 13, 1239–1279, doi:10.3762/bjoc.13.123
- transglycosylations are available in a review by Nogushi, et al. [70]. 4.1.2 Synthesis of glycosyl azides, dithiocarbamates, and thiols: Shoda and colleagues have also shown that when using similar conditions to those described above in the presence of certain nucleophiles glycosyl azides [73], dithiocarbamates [74
Graphical Abstract
Scheme 1: Solution-state conformations of D-glucose.
Scheme 2: Enzymatic synthesis of oligosaccharides.
Scheme 3: Enzymatic synthesis of a phosphorylated glycoprotein containing a mannose-6-phosphate (M6P)-termina...
Scheme 4: A) Selected GTs-mediated syntheses of oligosaccharides and other biologically active glycosides. B)...
Scheme 5: Enzymatic synthesis of nucleosides.
Scheme 6: Fischer glycosylation strategies.
Scheme 7: The basis of remote activation (adapted from [37]).
Scheme 8: Classic remote activation employing a MOP donor to access α-anomeric alcohols, carboxylates, and ph...
Figure 1: Synthesis of monoprotected glycosides from a (3-bromo-2-pyridyloxy) β-D-glycopyranosyl donor under ...
Scheme 9: Plausible mechanism for the synthesis of α-galactosides. TBDPS = tert-butyldiphenylsilyl.
Scheme 10: Synthesis of the 6-O-monoprotected galactopyranoside donor for remote activation.
Scheme 11: UDP-galactopyranose mutase-catalyzed isomerization of UDP-Galp to UDP-Galf.
Scheme 12: Synthesis of the 1-thioimidoyl galactofuranosyl donor.
Scheme 13: Glycosylation of MeOH using a self-activating donor in the absence of an external activator. a) Syn...
Scheme 14: The classical Lewis acid-catalyzed glycosylation.
Figure 2: Unprotected glycosyl donors used for the Lewis acid-catalyzed protecting group-free glycosylation r...
Scheme 15: Four-step synthesis of the phenyl β-galactothiopyranosyl donor.
Scheme 16: Protecting-group-free C3′-regioselective glycosylation of sucrose with α–F Glc.
Scheme 17: Synthesis of the α-fluoroglucosyl donor.
Figure 3: Protecting-group-free glycosyl donors and acceptors used in the Au(III)-catalyzed glycosylation.
Scheme 18: Synthesis of the mannosyl donor used in the study [62].
Scheme 19: The Pd-catalyzed stereoretentive glycosylation of arenes using anomeric stannane donors.
Scheme 20: Preparation of the protecting-group-free α and β-stannanes from advanced intermediates for stereoch...
Figure 4: Selective anomeric activating agents providing donors for direct activation of the anomeric carbon.
Scheme 21: One-step access to sugar oxazolines or 1,6-anhydrosugars.
Scheme 22: Enzymatic synthesis of a chitoheptaose using a mutant chitinase.
Scheme 23: One-pot access to glycosyl azides [73], dithiocarbamates [74], and aryl thiols using DMC activation and sub...
Scheme 24: Plausible reaction mechanism.
Scheme 25: Protecting-group-free synthesis of anomeric thiols from unprotected 2-deoxy-2-N-acetyl sugars.
Scheme 26: Protein conjugation of TTL221-PentK with a hyaluronan hexasaccharide thiol.
Scheme 27: Proposed mechanism.
Scheme 28: Direct two-step one-pot access to glycoconjugates through the in situ formation of the glycosyl azi...
Scheme 29: DMC as a phosphate-activating moiety for the synthesis of diphosphates. aβ-1,4-galactose transferas...
Figure 5: Triazinylmorpholinium salts as selective anomeric activating agents.
Scheme 30: One-step synthesis of DBT glycosides from unprotected sugars in aqueous medium.
Scheme 31: Postulated mechanism for the stereoselective formation of α-glycosides.
Scheme 32: DMT-donor synthesis used for metal-catalyzed glycosylation of simple alcohols.
Figure 6: Protecting group-free synthesis of glycosyl sulfonohydrazides (GSH).
Figure 7: The use of GSHs to access 1-O-phosphoryl and alkyl glycosides. A) Glycosylation of aliphatic alcoho...
Scheme 33: A) Proposed mechanism of glycosylation. B) Proposed mechanism for stereoselective azidation of the ...
Scheme 34: Mounting GlcNAc onto a sepharose solid support through a GSH donor.
Scheme 35: Lawesson’s reagent for the formation of 1,2-trans glycosides.
Scheme 36: Protecting-group-free protein conjugation via an in situ-formed thiol glycoside [98].
Scheme 37: pH-Specific glycosylation to functionalize SAMs on gold.
Figure 8: Protecting-group-free availability of phenolic glycosides under Mitsunobu conditions. DEAD = diethy...
Scheme 38: Accessing hydroxyazobenzenes under Mitsunobu conditions for the study of photoswitchable labels. DE...
Scheme 39: Stereoselective protecting-group-free glycosylation of D-glucose to provide the β-glucosyl benzoic ...
Figure 9: Direct synthesis of pyranosyl nucleosides from unactivated and unprotected ribose using optimized M...
Figure 10: Direct synthesis of furanosyl nucleosides from 5-O-monoprotected ribose in a one-pot glycosylation–...
Figure 11: Synthesis of ribofuranosides using a monoprotected ribosyl donor via an anhydrose intermediate.
Figure 12: C5′-modified nucleosides available under our conditions.
Scheme 40: Plausible reaction mechanism for the formation of the anhydrose.
Figure 13: Direct glycosylation of several aliphatic alcohols using catalytic Ti(Ot-Bu)4 in the presence of D-...
Figure 14: Access to glycosides using catalytic PPh3 and CBr4.
Figure 15: Access to ribofuranosyl glycosides as the major product under catalytic conditions. aLiOCl4 (2.0 eq...
Antibacterial structure–activity relationship studies of several tricyclic sulfur-containing flavonoids
- Lucian G. Bahrin,
- Henning Hopf,
- Peter G. Jones,
- Laura G. Sarbu,
- Cornelia Babii,
- Alina C. Mihai,
- Marius Stefan and
- Lucian M. Birsa
Beilstein J. Org. Chem. 2016, 12, 1065–1071, doi:10.3762/bjoc.12.100
- . Fluorine-substituted flavonoids were found to be less active than those bearing other halogen atoms. Keywords: antibacterial activity; dithiocarbamates; dithiolium salts; flavonoids; SAR studies; Introduction The extensive use of antibiotics in human treatment and agriculture has led to the development
Graphical Abstract
Figure 1: The molecular structure of tricyclic flavonoid 1.
Scheme 1: Synthesis of flavanones 4a–m and tricyclic flavonoids 5a–m. Conditions: i) EtOH, reflux, 4 h; ii) H2...
Figure 2: The syn and anti-isomers of flavanones 4.
Figure 3: Molecular structures of 4d (left) and 4f (right). Ellipsoids represent 50% probability levels [24].
Figure 4: Molecular structure of 5a (left, both independent molecules) and 5b (right, one of two independent ...
[2.2]Paracyclophane derivatives containing tetrathiafulvalene moieties
- Laura G. Sarbu,
- Lucian G. Bahrin,
- Peter G. Jones,
- Lucian M. Birsa and
- Henning Hopf
Beilstein J. Org. Chem. 2015, 11, 1917–1921, doi:10.3762/bjoc.11.207
- -yl)-1,3-dithiol-2-thione in the presence of trimethylphosphite. The 1,3-dithiol-2-thione derivative was in turn synthesized by the regioselective bromination of 4-acetyl[2.2]paracyclophane, then through the corresponding dithiocarbamates and 1,3-dithiolium salts. Keywords: dithiocarbamates; 1,3
- , represent an accessible route to variously substituted phenacyl carbodithioates [19]. Following this synthetic protocol, we obtained dithiocarbamates 4a–c by reacting 2-bromo-1-([2.2]paracyclophan-4-yl)ethan-1-one (2) with sodium N,N-dimethyldithiocarbamate (3a), pyrrolidinium pyrolidine-1-carbodithioate
- (3b) and morpholinium morpholine-4-carbodithioate (3c), respectively. These compounds were obtained as colorless crystals in 80% isolated yields. The structures of dithiocarbamates 4a–c were inferred from their analytical and spectral data; thus the 1H NMR spectra include the expected signals for the
Graphical Abstract
Scheme 1: Synthesis of 2-N,N-dialkylamino-4-([2.2]paracyclophan-4-yl)-1,3-dithiol-2-ylium perchlorates 5.
Figure 1: Molecular structure of compound 4a. Ellipsoids represent 30% probability levels. Selected molecular...
Scheme 2: Synthesis of tetrathiafulvalenes 7.
Figure 2: Molecular structure of compound 6 (two independent molecules). Ellipsoids represent 30% probability...
Tricyclic flavonoids with 1,3-dithiolium substructure
- Lucian G. Bahrin,
- Peter G. Jones and
- Henning Hopf
Beilstein J. Org. Chem. 2012, 8, 1999–2003, doi:10.3762/bjoc.8.226
- Chemistry, Technical University of Braunschweig, Hagenring 30, D-38106 Braunschweig, Germany 10.3762/bjoc.8.226 Abstract The synthesis of new 3-dithiocarbamic flavonoids has been accomplished by the reaction of the corresponding 2-hydroxyaryl dithiocarbamates with aminals. These flavonoids were obtained as
- a mixture of diastereoisomers, the anti isomer being the major one. The heterocyclization of these compounds provided novel tricyclic flavonoids bearing a 1,3-dithiolium-2-yl ring fused at the 3,4-carbon positions of the benzopyran moiety. Keywords: aminals; benzopyrans; dithiocarbamates
- flavonoids bearing a 1,3-dithiolium-2-yl ring fused at the 3,4-carbon positions of the benzopyran moiety, utilizing the heterocyclization of corresponding 3-substituted dithiocarbamic flavonones. Results and Discussion The treatment of several dithiocarbamates of type 4 with aminals has been reported to
Graphical Abstract
Figure 1: Polycyclic flavonoids.
Scheme 1: The synthesis of flavonoids 6 and 7.
Figure 2: Diastereoisomers of flavonoids 6.
Figure 3: Molecular structure of flavonoid 6a in the solid state. Ellipsoids represent 50% probability levels...
Figure 4: Molecular structure of flavonoid 6b in the solid state. Ellipsoids represent 50% probability levels...
Figure 5: Molecular structure of flavonoid 7a in the solid state. Ellipsoids represent 50% probability levels....
A general and facile one-pot process of isothiocyanates from amines under aqueous conditions
- Nan Sun,
- Bin Li,
- Jianping Shao,
- Weimin Mo,
- Baoxiang Hu,
- Zhenlu Shen and
- Xinquan Hu
Beilstein J. Org. Chem. 2012, 8, 61–70, doi:10.3762/bjoc.8.6
- . Recently, a two-step approach, which was named reagent-promoted desulfurylation of dithiocarbamates strategy, has attracted much attention. In the context of this method, an amine is typically converted into a corresponding dithiocarbamate by reacting with CS2 in the presence of a base; and a subsequent
- , we speculated that it could also be effective and practical in the desulfurylation of dithiocarbamates to form isothiocyanates. Our initial study started with aniline (1, Scheme 1) to prepare phenyl isothiocyanate (4, Scheme 1) via N-phenyl dithiocarbamate (2-1, Scheme 1) followed by desulfurylation
- with TCT. Because inorganic bases were more efficient during the conversion of arylamines to N-aryl dithiocarbamates in aqueous systems [54][55][56][57][58][59], we chose inorganic bases to screen the optimal reaction conditions for the one-pot synthesis of 4. Following the literature procedure, N
Graphical Abstract
Scheme 1: The proposed process for the formation of N-phenyl isothiocyanate from aniline.
