Search for "in situ generation" in Full Text gives 133 result(s) in Beilstein Journal of Organic Chemistry.
Beilstein J. Org. Chem. 2019, 15, 1786–1794, doi:10.3762/bjoc.15.172
Graphical Abstract
Scheme 1: Oxidation of 3-pheny-1-propanol (1a) with N-chlorosuccinimide (NCS) in the presence of (2,2,6,6-tet...
Scheme 2: Hypothesized pathways for the TEMPO-assisted oxidation of alcohols in a) basic or b) acidic reactio...
Scheme 3: TEMPO-assisted oxidation of 3-pheny-1-propanol (1a) under mechanical activation conditions. aPercen...
Scheme 4: Scope of primary alcohol oxidation under mechanical activation conditions. aAll yields refer to iso...
Scheme 5: Proposed mechanism for the oxidation of benzylic alcohols 6a and 7a under mechanochemical condition...
Scheme 6: Scope of secondary alcohols in the oxidation under mechanical activation conditions. aAll yields re...
Scheme 7: Possible mechanism for the TEMPO-mediated oxidation of primary and secondary alcohols by using NaOC...
Beilstein J. Org. Chem. 2019, 15, 1612–1704, doi:10.3762/bjoc.15.165
Graphical Abstract
Figure 1: Various drugs having IP nucleus.
Figure 2: Participation percentage of various TMs for the syntheses of IPs.
Scheme 1: CuI–NaHSO4·SiO2-catalyzed synthesis of imidazo[1,2-a]pyridines.
Scheme 2: Experimental examination of reaction conditions.
Scheme 3: One-pot tandem reaction for the synthesis of 2-haloimidazopyridines.
Scheme 4: Mechanistic scheme for the synthesis of 2-haloimidazopyridine.
Scheme 5: Copper-MOF-catalyzed three-component reaction (3-CR) for imidazo[1,2-a]pyridines.
Scheme 6: Mechanism for copper-MOF-driven synthesis.
Scheme 7: Heterogeneous synthesis via titania-supported CuCl2.
Scheme 8: Mechanism involving oxidative C–H functionalization.
Scheme 9: Heterogeneous synthesis of IPs.
Scheme 10: One-pot regiospecific synthesis of imidazo[1,2-a]pyridines.
Scheme 11: Vinyl azide as an unprecedented substrate for imidazo[1,2-a]pyridines.
Scheme 12: Radical pathway.
Scheme 13: Cu(I)-catalyzed transannulation approach for imidazo[1,5-a]pyridines.
Scheme 14: Plausible radical pathway for the synthesis of imidazo[1,5-a]pyridines.
Scheme 15: A solvent-free domino reaction for imidazo[1,2-a]pyridines.
Scheme 16: Cu-NPs-mediated synthesis of imidazo[1,2-a]pyridines.
Scheme 17: CuI-catalyzed synthesis of isoxazolylimidazo[1,2-a]pyridines.
Scheme 18: Functionalization of 4-bromo derivative via Sonogashira coupling reaction.
Scheme 19: A plausible reaction pathway.
Scheme 20: Cu(I)-catalyzed intramolecular oxidative C–H amidation reaction.
Scheme 21: One-pot synthetic reaction for imidazo[1,2-a]pyridine.
Scheme 22: Plausible reaction mechanism.
Scheme 23: Cu(OAc)2-promoted synthesis of imidazo[1,2-a]pyridines.
Scheme 24: Mechanism for aminomethylation/cycloisomerization of propiolates with imines.
Scheme 25: Three-component synthesis of imidazo[1,2-a]pyridines.
Figure 3: Scope of pyridin-2(1H)-ones and acetophenones.
Scheme 26: CuO NPS-promoted A3 coupling reaction.
Scheme 27: Cu(II)-catalyzed C–N bond formation reaction.
Scheme 28: Mechanism involving Chan–Lam/Ullmann coupling.
Scheme 29: Synthesis of formyl-substituted imidazo[1,2-a]pyridines.
Scheme 30: A tandem sp3 C–H amination reaction.
Scheme 31: Probable mechanistic approach.
Scheme 32: Dual catalytic system for imidazo[1,2-a]pyridines.
Scheme 33: Tentative mechanism.
Scheme 34: CuO/CuAl2O4/ᴅ-glucose-promoted 3-CCR.
Scheme 35: A tandem CuOx/OMS-2-based synthetic strategy.
Figure 4: Biomimetic catalytic oxidation in the presence of electron-transfer mediators (ETMs).
Scheme 36: Control experiment.
Scheme 37: Copper-catalyzed C(sp3)–H aminatin reaction.
Scheme 38: Reaction of secondary amines.
Scheme 39: Probable mechanistic pathway.
Scheme 40: Coupling reaction of α-azidoketones.
Scheme 41: Probable pathway.
Scheme 42: Probable mechanism with free energy calculations.
Scheme 43: MCR for cyanated IP synthesis.
Scheme 44: Substrate scope for the reaction.
Scheme 45: Reaction mechanism.
Scheme 46: Probable mechanistic pathway for Cu/ZnAl2O4-catalyzed reaction.
Scheme 47: Copper-catalyzed double oxidative C–H amination reaction.
Scheme 48: Application towards different coupling reactions.
Scheme 49: Reaction mechanism.
Scheme 50: Condensation–cyclization approach for the synthesis of 1,3-diarylated imidazo[1,5-a]pyridines.
Scheme 51: Optimized reaction conditions.
Scheme 52: One-pot 2-CR.
Scheme 53: One-pot 3-CR without the isolation of chalcone.
Scheme 54: Copper–Pybox-catalyzed cyclization reaction.
Scheme 55: Mechanistic pathway catalyzed by Cu–Pybox complex.
Scheme 56: Cu(II)-promoted C(sp3)-H amination reaction.
Scheme 57: Wider substrate applicability for the reaction.
Scheme 58: Plausible reaction mechanism.
Scheme 59: CuI assisted C–N cross-coupling reaction.
Scheme 60: Probable reaction mechanism involving sp3 C–H amination.
Scheme 61: One-pot MCR-catalyzed by CoFe2O4/CNT-Cu.
Scheme 62: Mechanistic pathway.
Scheme 63: Synthetic scheme for 3-nitroimidazo[1,2-a]pyridines.
Scheme 64: Plausible mechanism for CuBr-catalyzed reaction.
Scheme 65: Regioselective synthesis of halo-substituted imidazo[1,2-a]pyridines.
Scheme 66: Synthesis of 2-phenylimidazo[1,2-a]pyridines.
Scheme 67: Synthesis of diarylated compounds.
Scheme 68: CuBr2-mediated one-pot two-component oxidative coupling reaction.
Scheme 69: Decarboxylative cyclization route to synthesize 1,3-diarylimidazo[1,5-a]pyridines.
Scheme 70: Mechanistic pathway.
Scheme 71: C–H functionalization reaction of enamines to produce diversified heterocycles.
Scheme 72: A plausible mechanism.
Scheme 73: CuI-promoted aerobic oxidative cyclization reaction of ketoxime acetates and pyridines.
Scheme 74: CuI-catalyzed pathway for the formation of imidazo[1,2-a]pyridine.
Scheme 75: Mechanistic pathway.
Scheme 76: Mechanistic rationale for the synthesis of products.
Scheme 77: Copper-catalyzed synthesis of vinyloxy-IP.
Scheme 78: Regioselective product formation with propiolates.
Scheme 79: Proposed mechanism for vinyloxy-IP formation.
Scheme 80: Regioselective synthesis of 3-hetero-substituted imidazo[1,2-a]pyridines with different reaction su...
Scheme 81: Mechanistic pathway.
Scheme 82: CuI-mediated synthesis of 3-formylimidazo[1,2-a]pyridines.
Scheme 83: Radical pathway for 3-formylated IP synthesis.
Scheme 84: Pd-catalyzed urea-cyclization reaction for IPs.
Scheme 85: Pd-catalyzed one-pot-tandem amination and intramolecular amidation reaction.
Figure 5: Scope of aniline nucleophiles.
Scheme 86: Pd–Cu-catalyzed Sonogashira coupling reaction.
Scheme 87: One-pot amide coupling reaction for the synthesis of imidazo[4,5-b]pyridines.
Scheme 88: Urea cyclization reaction for the synthesis of two series of pyridines.
Scheme 89: Amidation reaction for the synthesis of imidazo[4,5-b]pyridines.
Figure 6: Amide scope.
Scheme 90: Pd NPs-catalyzed 3-component reaction for the synthesis of 2,3-diarylated IPs.
Scheme 91: Plausible mechanistic pathway for Pd NPs-catalyzed MCR.
Scheme 92: Synthesis of chromenoannulated imidazo[1,2-a]pyridines.
Scheme 93: Mechanism for the synthesis of chromeno-annulated IPs.
Scheme 94: Zinc oxide NRs-catalyzed synthesis of imidazo[1,2-a]azines/diazines.
Scheme 95: Zinc oxide-catalyzed isocyanide based GBB reaction.
Scheme 96: Reaction pathway for ZnO-catalyzed GBB reaction.
Scheme 97: Mechanistic pathway.
Scheme 98: ZnO NRs-catalyzed MCR for the synthesis of imidazo[1,2-a]azines.
Scheme 99: Ugi type GBB three-component reaction.
Scheme 100: Magnetic NPs-catalyzed synthesis of imidazo[1,2-a]pyridines.
Scheme 101: Regioselective synthesis of 2-alkoxyimidazo[1,2-a]pyridines catalyzed by Fe-SBA-15.
Scheme 102: Plausible mechanistic pathway for the synthesis of 2-alkoxyimidazopyridine.
Scheme 103: Iron-catalyzed synthetic approach.
Scheme 104: Iron-catalyzed aminooxygenation reaction.
Scheme 105: Mechanistic pathway.
Scheme 106: Rh(III)-catalyzed double C–H activation of 2-substituted imidazoles and alkynes.
Scheme 107: Plausible reaction mechanism.
Scheme 108: Rh(III)-catalyzed non-aromatic C(sp2)–H bond activation–functionalization for the synthesis of imid...
Scheme 109: Reactivity and selectivity of different substrates.
Scheme 110: Rh-catalyzed direct C–H alkynylation by Li et al.
Scheme 111: Suggested radical mechanism.
Scheme 112: Scandium(III)triflate-catalyzed one-pot reaction and its mechanism for the synthesis of benzimidazo...
Scheme 113: RuCl3-assisted Ugi-type Groebke–Blackburn condensation reaction.
Scheme 114: C-3 aroylation via Ru-catalyzed two-component reaction.
Scheme 115: Regioselective synthetic mechanism.
Scheme 116: La(III)-catalyzed one-pot GBB reaction.
Scheme 117: Mechanistic approach for the synthesis of imidazo[1,2-a]pyridines.
Scheme 118: Synthesis of imidazo[1,2-a]pyridine using LaMnO3 NPs under neat conditions.
Scheme 119: Mechanistic approach.
Scheme 120: One-pot 3-CR for regioselective synthesis of 2-alkoxy-3-arylimidazo[1,2-a]pyridines.
Scheme 121: Formation of two possible products under optimization of the catalysts.
Scheme 122: Mechanistic strategy for NiFe2O4-catalyzed reaction.
Scheme 123: Two-component reaction for synthesizing imidazodipyridiniums.
Scheme 124: Mechanistic scheme for the synthesis of imidazodipyridiniums.
Scheme 125: CuI-catalyzed arylation of imidazo[1,2-a]pyridines.
Scheme 126: Mechanism for arylation reaction.
Scheme 127: Cupric acetate-catalyzed double carbonylation approach.
Scheme 128: Radical mechanism for double carbonylation of IP.
Scheme 129: C–S bond formation reaction catalyzed by cupric acetate.
Scheme 130: Cupric acetate-catalyzed C-3 formylation approach.
Scheme 131: Control experiments for signifying the role of DMSO and oxygen.
Scheme 132: Mechanism pathway.
Scheme 133: Copper bromide-catalyzed CDC reaction.
Scheme 134: Extension of the substrate scope.
Scheme 135: Plausible radical pathway.
Scheme 136: Transannulation reaction for the synthesis of imidazo[1,5-a]pyridines.
Scheme 137: Plausible reaction pathway for denitrogenative transannulation.
Scheme 138: Cupric acetate-catalyzed C-3 carbonylation reaction.
Scheme 139: Plausible mechanism for regioselective C-3 carbonylation.
Scheme 140: Alkynylation reaction at C-2 of 3H-imidazo[4,5-b]pyridines.
Scheme 141: Two-way mechanism for C-2 alkynylation of 3H-imidazo[4,5-b]pyridines.
Scheme 142: Palladium-catalyzed SCCR approach.
Scheme 143: Palladium-catalyzed Suzuki coupling reaction.
Scheme 144: Reaction mechanism.
Scheme 145: A phosphine free palladium-catalyzed synthesis of C-3 arylated imidazopyridines.
Scheme 146: Palladium-mediated Buchwald–Hartwig cross-coupling reaction.
Figure 7: Structure of the ligands optimized.
Scheme 147: Palladium acetate-catalyzed direct arylation of imidazo[1,2-a]pyridines.
Scheme 148: Palladium acetate-catalyzed mechanistic pathway.
Scheme 149: Palladium acetate-catalyzed regioselective arylation reported by Liu and Zhan.
Scheme 150: Mechanism for selective C-3 arylation of IP.
Scheme 151: Pd(II)-catalyzed alkenylation reaction with styrenes.
Scheme 152: Pd(II)-catalyzed alkenylation reaction with acrylates.
Scheme 153: A two way mechanism.
Scheme 154: Double C–H activation reaction catalyzed by Pd(OAc)2.
Scheme 155: Probable mechanism.
Scheme 156: Palladium-catalyzed decarboxylative coupling.
Scheme 157: Mechanistic cycle for decarboxylative arylation reaction.
Scheme 158: Ligand-free approach for arylation of imidazo[1,2-a]pyridine-3-carboxylic acids.
Scheme 159: Mechanism for ligandless arylation reaction.
Scheme 160: NHC-Pd(II) complex assisted arylation reaction.
Scheme 161: C-3 arylation of imidazo[1,2-a]pyridines with aryl bromides catalyzed by Pd(OAc)2.
Scheme 162: Pd(II)-catalyzed C-3 arylations with aryl tosylates and mesylates.
Scheme 163: CDC reaction for the synthesis of imidazo[1,2-a]pyridines.
Scheme 164: Plausible reaction mechanism for Pd(OAc)2-catalyzed synthesis of imidazo[1,2-a]pyridines.
Scheme 165: Pd-catalyzed C–H amination reaction.
Scheme 166: Mechanism for C–H amination reaction.
Scheme 167: One-pot synthesis for 3,6-di- or 2,3,6-tri(hetero)arylimidazo[1,2-a]pyridines.
Scheme 168: C–H/C–H cross-coupling reaction of IPs and azoles catalyzed by Pd(II).
Scheme 169: Mechanistic cycle.
Scheme 170: Rh-catalyzed C–H arylation reaction.
Scheme 171: Mechanistic pathway for C–H arylation of imidazo[1,2-a]pyridine.
Scheme 172: Rh(III)-catalyzed double C–H activation of 2-phenylimidazo[1,2-a]pyridines and alkynes.
Scheme 173: Rh(III)-catalyzed mechanistic pathway.
Scheme 174: Rh(III)-mediated oxidative coupling reaction.
Scheme 175: Reactions showing functionalization of the product obtained by the group of Kotla.
Scheme 176: Mechanism for Rh(III)-catalyzed oxidative coupling reaction.
Scheme 177: Rh(III)-catalyzed C–H activation reaction.
Scheme 178: Mechanistic cycle.
Scheme 179: Annulation reactions of 2-arylimidazo[1,2-a]pyridines and alkynes.
Scheme 180: Two-way reaction mechanism for annulations reaction.
Scheme 181: [RuCl2(p-cymene)]2-catalyzed C–C bond formation reaction.
Scheme 182: Reported reaction mechanism.
Scheme 183: Fe(III) catalyzed C-3 formylation approach.
Scheme 184: SET mechanism-catalyzed by Fe(III).
Scheme 185: Ni(dpp)Cl2-catalyzed KTC coupling.
Scheme 186: Pd-catalyzed SM coupling.
Scheme 187: Vanadium-catalyzed coupling of IP and NMO.
Scheme 188: Mechanistic cycle.
Scheme 189: Selective C3/C5–H bond functionalizations by mono and bimetallic systems.
Scheme 190: rGO-Ni@Pd-catalyzed C–H bond arylation of imidazo[1,2-a]pyridine.
Scheme 191: Mechanistic pathway for heterogeneously catalyzed arylation reaction.
Scheme 192: Zinc triflate-catalyzed coupling reaction of substituted propargyl alcohols.
Beilstein J. Org. Chem. 2019, 15, 1061–1064, doi:10.3762/bjoc.15.103
Graphical Abstract
Figure 1: Examples of imidazole (1 and 2) and oxazole (3) syntheses from propargylamides previously reported ...
Figure 2: Substrate scope for the three-component synthesis of 5.
Figure 3: Plausible mechanism for the formation of 5.
Beilstein J. Org. Chem. 2019, 15, 610–616, doi:10.3762/bjoc.15.56
Graphical Abstract
Scheme 1: Structures of scorzodihydrostilbenes A–E (1–5) and resveratrol.
Scheme 2: Synthesis of dihydrostilbenes 8a–d by ruthenium-catalyzed addition of ketones 6 to styrenes 7. Yiel...
Scheme 3: Cleavage of benzyl protecting groups in ketones 8a and 8b. Synthesis of scorzodihydrostilbene aglyc...
Scheme 4: Synthesis of glycoside 12 and deprotected epi-scorzodihydrostilbene D (13). Yields of isolated prod...
Beilstein J. Org. Chem. 2019, 15, 497–505, doi:10.3762/bjoc.15.43
Graphical Abstract
Scheme 1: Synthesis of 2-unsubstituted imidazole N-oxides 1 from α-hydroxyiminoketones 2 and formaldimines 3.
Scheme 2: Preparation of adamantyloxyamine (4) and its conversion into N-(adamantyloxy)formaldimine (6a); Ad ...
Scheme 3: Synthesis of 1-(adamantyloxy)imidazole 3-oxides 7a–e and 1-adamantylimidazole 3-oxides 7f,g in acet...
Scheme 4: Deoxygenation of 1-(adamantyloxy)imidazole 3-oxides 7a–d and isomerization of 7b into imidazole-2-o...
Scheme 5: Conversions of imidazole 3-oxides 7a–d into 1-(adamantyloxy)imidazole-2-thiones 10a–d via sulfur tr...
Scheme 6: Syntheses of the non-symmetric 1,3-dialkoxyimidazolium bromides 13a–c and 1-alkyl-3-alkoxyimidazoli...
Scheme 7: Attempted O-adamantylation of imidazole N-oxide 7a with adamantan-1-yl trifluoroacetate and subsequ...
Scheme 8: Synthesis of the symmetric 1,3-di(adamantyloxy)imidazolium bromide (15) and its transformation to 1...
Beilstein J. Org. Chem. 2019, 15, 401–430, doi:10.3762/bjoc.15.36
Graphical Abstract
Figure 1: Structural formulas of Nam, NA, NR+, NMN, and NAD+.
Figure 2: Main synthetic routes to nicotinamide riboside (NR+X−).
Scheme 1: Synthesis of NR+Cl− based on the reaction of peracylated chlorosugars with Nam.
Figure 3: Predominant formation of β-anomer over α-anomer of NR+X−.
Scheme 2: Synthesis of NR+Cl− by reacting 3,5-di-O-benzoyl-D-ribofuranosyl chloride (5) with Nam (1a).
Figure 4: Mechanism of the formation of the β-anomer of the glycosylated product in the case of the reaction ...
Scheme 3: Synthesis of NR+Br− by reacting bromosugars with Nam (1a).
Scheme 4: Synthesis of NR+OTf− based on the glycosylation of Nam (1a) with tetra-O-acetyl-β-D-ribofuranose (2a...
Scheme 5: Improved synthesis of NR+OTfˉ and NAR+OTfˉ based on the glycosylation of pre-silylated Nam or NA wi...
Scheme 6: Synthesis of triacetylated NAR+OTf− by glycosylation of nicotinic acid trimethylsilyl ester with te...
Scheme 7: Synthesis of NR+Cl− from NR+OTf− by means of ion exchange with sodium chloride solution.
Scheme 8: Synthesis of acylated NR+OTf− by means of ion exchange with sodium chloride.
Scheme 9: Synthesis of triacetylated derivatives of NAR+ by glycosylation of nicotinic acid esters with ribos...
Scheme 10: Synthesis of NR+OTf− from the triflate salt of ethyl nicotinate-2,3,5-triacetyl-β-D-riboside in met...
Scheme 11: Reaction of 2,3,5-tri-O-acetyl-β-phenyl nicotinate riboside triflate salt with secondary and tertia...
Scheme 12: Synthesis of NMN based on the Zincke reaction of N-(2,4-dinitrophenyl)-3-carbamoylpyridinium chlori...
Scheme 13: Synthesis of NMN based on the Zincke reaction of N-(2,4-dinitrophenyl)-3-carbamoylpyridinium chlori...
Scheme 14: Efficacious protection of 2′,3′-hydroxy groups of NR+X−.
Scheme 15: Protection of the 2′,3′-hydroxy groups of NR+Cl– with a mesitylmethylene acetal group.
Figure 5: Reduction of derivatives of NR+Xˉ into corresponding 1,2-; 1,4-; 1,6-NRH derivatives.
Figure 6: Mechanism of the reduction of the pyridinium core with dithionite as adapted from [67].
Scheme 16: Reduction of triacylated NR+OTf– derivatives by sodium dithionite followed by complete removal of a...
Figure 7: Structural formulas of iridium and rhodium catalysts (a)–(d) for regeneration of NAD(P)H from NAD(P)...
Figure 8: Two approaches to synthesis of 5′-derivatives of NR+.
Scheme 17: Synthesis of NMN starting from NR+ salt.
Scheme 18: Efficient synthesis of NMN by phosphorylation of 2′,3′-O-isopropylidene-NR+ triflate followed by re...
Scheme 19: Synthesis of a bisphosphonate analogue of β-NAD+ based on DCC-induced conjugation of 2′,3′-O-isopro...
Scheme 20: Synthesis of 5′-acyl and 2′,3′,5′-triacyl derivatives of NR+.
Figure 9: Structural formulas of NMN analogues 39–41.
Scheme 21: Synthesis of 5′-phosphorylated derivatives of NR+ using a “reduction–modification–oxidation” approa...
Scheme 22: Synthesis of 5′-phosphorylated derivatives of NR+ using a “reduction–modification–reoxidation” appr...
Figure 10: Structural formulas of 5′-phosphorylated derivatives of NR+.
Scheme 23: Synthesis of 5′-phosphorylated derivatives of NR+ using a direct NR+ phosphorylation approach.
Figure 11: Structural formulas of amino acid NR+ conjugates.
Scheme 24: Synthesis of amino acid NR+ conjugates using NRH and protected amino acid under CDI-coupling condit...
Figure 12: Chemical structures of known isotopically labelled NR+ analogues and derivatives.
Scheme 25: Synthesis of [2′-3H]-NR+ and [2′-3H]-NMN.
Scheme 26: Synthesis of α- and β-anomers of [1′-2H]-NMN.
Beilstein J. Org. Chem. 2018, 14, 3025–3046, doi:10.3762/bjoc.14.282
Graphical Abstract
Figure 1: Typical oxidative and reductive cycle for a photoredox catalyst (PC).
Figure 2: Transitions involved in absorbing species containing π, σ and n electrons.
Figure 3: Ligand to metal charge transfer (illustrated here for a d6 metal complex).
Figure 4: Metal to ligand charge transfer (illustrated here for a d5 metal complex).
Scheme 1: Structures of additives involved in the photoredox catalytic cycles.
Figure 5: Catalytic cycles involved with iodonium salt and (A) (TMS)3SiH, (B) NVK and (C) EDB.
Scheme 2: Structures of photoredox metal-based catalysts.
Scheme 3: Photocatalytical cycle for the Ru complex.
Scheme 4: Structures of photoredox organocatalysts.
Scheme 5: Diversity of the chemical structures of photoredox organocatalysts.
Scheme 6: Structures of benchmarked monomers.
Scheme 7: Structure of the CARET additive.
Scheme 8: Photoredox catalysis mechanism of a visible light-mediated living radical polymerization. (Abbrevia...
Beilstein J. Org. Chem. 2018, 14, 2999–3010, doi:10.3762/bjoc.14.279
Graphical Abstract
Scheme 1: Synthesis of first Ru-dithiolate metathesis catalysts.
Figure 1: Most efficient Ru-dithiolate catalysts for stereoretentive olefin metathesis with Z- and E-alkenes ...
Figure 2: Selected examples of sterically or electronically modified ruthenium dithiolate complexes.
Figure 3: Model for stereoretentive metathesis proposed by Pederson and Grubbs [3].
Figure 4: Decrease in the benzylidene signal over time upon reaction with (E)-2-hexenyl acetate.
Scheme 2: Selected applications, part 1.
Scheme 3: Selected applications, part 2.
Figure 5: Catalyst loading required for different types of metathesis reactions.
Scheme 4: Proposed catalyst decomposition pathway occurring via attack of the electron-rich sulfide into meth...
Scheme 5: In situ methylene capping strategy for stereoretentive metathesis.
Scheme 6: Stereoretentive cross-metathesis with (Z)-butene (Z-25) as in situ methylene capping agent; selecte...
Scheme 7: Cross metathesis with Z- and E-trisubstituted allylic alcohols.
Scheme 8: In situ synthesis of Ru-3 and application thereof in the cross-metathesis of 12 and 50.
Figure 6: Examples of biologically active and fragrance molecules synthesized by stereoretentive metathesis.
Beilstein J. Org. Chem. 2018, 14, 2916–2922, doi:10.3762/bjoc.14.270
Graphical Abstract
Scheme 1: General methods for the synthesis of triazoles.
Scheme 2: Substrate scope of the terminal alkynes. Conditions: 1 (0.5 mmol), 2a (0.75 mmol), TMSN3 (0.75 mmol...
Scheme 3: Substrate scope of the alkyl diacyl peroxides. Conditions: 1a (0.5 mmol), 2 (0.75 mmol), TMSN3 (0.7...
Scheme 4: Preliminary mechanistic studies.
Scheme 5: Plausible reaction mechanism.
Beilstein J. Org. Chem. 2018, 14, 2722–2729, doi:10.3762/bjoc.14.250
Graphical Abstract
Scheme 1: Our synthetic plan for pyrrolo[3,2-c]azepines.
Scheme 2: Preparation of precursors for the Pummerer reactions.
Scheme 3: Substrate scope of 1,7-S and 1,7-Se shift reactions.
Scheme 4: Proposed mechanism.
Scheme 5: Crossover experiment.
Scheme 6: Lewis acid-catalysed cyclization of diols.
Scheme 7: Sequential process of sulfanyl-1,6-diyne 1 to 4H-pyrrolo[3,4-g]oxazine 25g.
Beilstein J. Org. Chem. 2018, 14, 2308–2312, doi:10.3762/bjoc.14.205
Graphical Abstract
Scheme 1: One-pot synthesis of epoxides from benzyl alcohols and aldehydes.
Figure 1: Scope of the one-pot synthesis of epoxides from benzyl alcohols and aldehydes.
Scheme 2: mCPBA epoxidation of electron-rich stilbene derivatives.
Figure 2: Scope of the reaction with electron-rich alcohols and aldehydes.
Beilstein J. Org. Chem. 2018, 14, 2220–2228, doi:10.3762/bjoc.14.196
Graphical Abstract
Figure 1: Continuous-flow process to produce and react N-chloramines.
Figure 2: Left: Laboratory scale CSTR developed by our group [8]. Right: 5-stage CSTR configuration using co-fee...
Figure 3: Continuous-flow amide 18 formation using 1-stage CSTR. Blue squares: FeCl3 included; red circles: F...
Scheme 1: Continuous-flow transfer hydrogenation of in situ generated imines.
Beilstein J. Org. Chem. 2018, 14, 1854–1858, doi:10.3762/bjoc.14.159
Graphical Abstract
Scheme 1: Previously reported preparation of IBS (1) [17].
Scheme 2: Oxidation of 2-iodobenzenesulfonate 5 by Oxone in water.
Figure 1: X-ray structure of an independent crystal unit of IBS 6-K.
Figure 2: Simplified representation of structure 6-K. Selected interatomic distances (Å): I(1)=O(1) 1.79; I(1...
Scheme 3: Comparison of the oxidation of sodium 2-iodobenzenesulfonate (5) with NaIO4 and 2-iodobenzenesulfon...
Beilstein J. Org. Chem. 2018, 14, 1813–1825, doi:10.3762/bjoc.14.154
Graphical Abstract
Figure 1: The structures of hypervalent iodine (III) reagents [8].
Scheme 1: Hypervalent iodine(III)-catalyzed functionalization of alkenes.
Scheme 2: Catalytic sulfonyloxylactonization of alkenoic acids [43].
Scheme 3: Catalytic diacetoxylation of alkenes [46].
Scheme 4: Intramolecular asymmetric dioxygenation of alkenes [48,50].
Scheme 5: Intermolecular asymmetric diacetoxylation of styrenes [52].
Scheme 6: Diacetoxylation of alkenes with ester groups containing catalysts 17 [55].
Scheme 7: Intramolecular diamination of alkenes [56].
Scheme 8: Intramolecular asymmetric diamination of alkenes [57].
Scheme 9: Intermolecular asymmetric diamination of alkenes [58].
Scheme 10: Iodoarene-catalyzed aminofluorination of alkenes [60,61].
Scheme 11: Iodoarene-catalyzed aminofluorination of alkenes [62].
Scheme 12: Catalytic difluorination of alkenes with Selectfluor [63].
Scheme 13: Iodoarene-catalyzed 1,2-difluorination of alkenes [64].
Scheme 14: Iodoarene-catalyzed asymmetric fluorination of styrenes [64,65].
Scheme 15: Gem-difluorination of styrenes [67].
Scheme 16: Asymmetric gem-difluorination of cinnamic acid derivatives [68].
Scheme 17: Oxyarylation of alkenes [71].
Scheme 18: Asymmetric oxidative rearrangements of alkenes [72].
Scheme 19: Bromolactonization of alkenes [75].
Scheme 20: Bromination of alkenes [77,78].
Scheme 21: Cooperative strategy for the carbonylation of alkenes [79].
Beilstein J. Org. Chem. 2018, 14, 1508–1528, doi:10.3762/bjoc.14.128
Graphical Abstract
Scheme 1: Strategies to address the issue of sustainability with polyvalent organoiodine reagents.
Scheme 2: Functionalization of ketones and alkenes with IBX.
Scheme 3: Functionalization of pyrroles with DMP.
Scheme 4: Catalytic benzoyloxy-trifluoromethylation reported by Szabó.
Scheme 5: Catalytic benzoyloxy-trifluoromethylation reported by Mideoka.
Scheme 6: Catalytic 1,4-benzoyloxy-trifluoromethylation of dienes.
Scheme 7: Catalytic benzoyloxy-trifluoromethylation of allylamines.
Scheme 8: Catalytic benzoyloxy-trifluoromethylation of enynes.
Scheme 9: Catalytic benzoyloxy-trifluoromethylation of allenes.
Scheme 10: Alkynylation of N-(aryl)imines with EBX for the formation of furans.
Scheme 11: Catalytic benzoyloxy-alkynylation of diazo compounds.
Scheme 12: Catalytic asymmetric benzoyloxy-alkynylation of diazo compounds.
Scheme 13: Catalytic 1,2-benzoyloxy-azidation of alkenes.
Scheme 14: Catalytic 1,2-benzoyloxy-azidation of enamides.
Scheme 15: Catalytic 1,2-benzoyloxy-iodination of alkenes.
Scheme 16: Seminal study with cyclic diaryl-λ3-iodane.
Scheme 17: Synthesis of alkylidenefluorenes from cyclic diaryl-λ3-iodanes.
Scheme 18: Synthesis of alkyne-substituted alkylidenefluorenes.
Scheme 19: Synthesis of phenanthrenes from cyclic diaryl-λ3-iodanes.
Scheme 20: Synthesis of dibenzocarbazoles from cyclic diaryl-λ3-iodanes.
Scheme 21: Synthesis of triazolophenantridines from cyclic diaryl-λ3-iodanes.
Scheme 22: Synthesis of functionalized benzoxazoles from cyclic diaryl-λ3-iodanes.
Scheme 23: Sequential difunctionalization of cyclic diaryl-λ3-iodanes.
Scheme 24: Double Suzuki–Miyaura coupling reaction of cyclic diaryl-λ3-iodanes.
Scheme 25: Synthesis of a δ-carboline from cyclic diaryl-λ3-iodane.
Scheme 26: Synthesis of N-(aryl)carbazoles from cyclic diaryl-λ3-iodanes.
Scheme 27: Synthesis of carbazoles from cyclic diaryl-λ3-iodanes.
Scheme 28: Synthesis of carbazoles and acridines from cyclic diaryl-λ3-iodanes.
Scheme 29: Synthesis of dibenzothiophenes from cyclic diaryl-λ3-iodanes.
Scheme 30: Synthesis of various sulfur heterocycles from cyclic diaryl-λ3-iodanes.
Scheme 31: Synthesis of dibenzothioheterocycles from cyclic diaryl-λ3-iodanes.
Scheme 32: Synthesis of dibenzosulfides and dibenzoselenides from cyclic diaryl-λ3-iodanes.
Scheme 33: Synthesis of dibenzosulfones from cyclic diaryl-λ3-iodanes.
Scheme 34: Seminal study with linear diaryl-λ3-iodanes.
Scheme 35: N-Arylation of benzotriazole with symmetrical diaryl-λ3-iodanes.
Scheme 36: Tandem catalytic C–H/N–H arylation of indoles with diaryl-λ3-iodanes.
Scheme 37: Tandem N-arylation/C(sp2)–H arylation with diaryl-λ3-iodanes.
Scheme 38: Catalytic intermolecular diarylation of anilines with diaryl-λ3-iodanes.
Scheme 39: Catalytic synthesis of diarylsulfides with diaryl-λ3-iodanes.
Scheme 40: α-Arylation of enolates using [bis(trifluoroacetoxy)iodo]arenes.
Scheme 41: Mechanism of the α-arylation using [bis(trifluoroacetoxy)iodo]arene.
Scheme 42: Catalytic nitrene additions mediated by [bis(acyloxy)iodo]arenes.
Scheme 43: Tandem of C(sp3)–H amination/sila-Sonogashira–Hagihara coupling.
Scheme 44: Tandem reaction using a λ3-iodane as an oxidant, a substrate and a coupling partner.
Scheme 45: Synthesis of 1,2-diarylated acrylamidines with ArI(OAc)2.
Beilstein J. Org. Chem. 2018, 14, 1317–1348, doi:10.3762/bjoc.14.113
Graphical Abstract
Scheme 1: Thermal reaction of sydnones with symmetrical alkynes.
Scheme 2: Reaction of sydnones with strained cycloalkynes.
Scheme 3: Reaction of sydnones with didehydrobenzenes.
Scheme 4: Formation of isomeric pyrazole dicarboxylates.
Scheme 5: Mechanism of thermal cycloaddition between sydnones and alkynes.
Scheme 6: Mechanism of photochemical reaction of sydnones with symmetrical alkynes.
Scheme 7: HOMO–LUMO diagram for thermal [3 + 2]-cycloaddition of sydnones with alkynes.
Scheme 8: Synthetic strategy leading to 1,2-disubstituted pyrazoles.
Scheme 9: Unsuccessful reaction with phenylpropiolic acid.
Scheme 10: Synthetic strategy leading to 1,4,5-trisubstituted pyrazoles.
Scheme 11: Reaction of sydnones carrying in position 4- six-membered 2-N-heterocyclic ring.
Scheme 12: Strain-promoted sydnone alkyne cycloaddition (SPSAC).
Scheme 13: Synthesis of a key intermediate of niraparib.
Scheme 14: Reaction of sydnones with 1,3-/1,4-benzdiyne equivalents.
Scheme 15: Reaction of sydnones with heterocyclic strained cycloalkynes.
Scheme 16: Mono-copper catalyzed cycloaddition reaction.
Scheme 17: Di-copper catalyzed cycloaddition reaction.
Beilstein J. Org. Chem. 2018, 14, 1263–1280, doi:10.3762/bjoc.14.108
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.
Beilstein J. Org. Chem. 2018, 14, 1244–1262, doi:10.3762/bjoc.14.107
Graphical Abstract
Scheme 1: An overview of different chiral iodine reagents or precursors thereof.
Scheme 2: Asymmetric oxidation of sulfides by chiral hypervalent iodine reagents.
Scheme 3: Oxidative dearomatization of naphthol derivatives by Kita et al.
Scheme 4: [4 + 2] Diels–Alder dimerization reported by Birman et al.
Scheme 5: m-CPBA guided catalytic oxidative naphthol dearomatization.
Scheme 6: Oxidative dearomatization of phenolic derivatives by Ishihara et al.
Scheme 7: Oxidative spirocyclization applying precatalyst 11 developed by Ciufolini et al.
Scheme 8: Asymmetric hydroxylative dearomatization.
Scheme 9: Enantioselective oxylactonization reported by Fujita et al.
Scheme 10: Dioxytosylation of styrene (47) by Wirth et al.
Scheme 11: Oxyarylation and aminoarylation of alkenes.
Scheme 12: Asymmetric diamination of alkenes.
Scheme 13: Stereoselective oxyamination of alkenes reported by Wirth et al.
Scheme 14: Enantioselective and regioselective aminofluorination by Nevado et al.
Scheme 15: Fluorinated difunctionalization reported by Jacobsen et al.
Scheme 16: Aryl rearrangement reported by Wirth et al.
Scheme 17: α-Arylation of β-ketoesters.
Scheme 18: Asymmetric α-oxytosylation of carbonyls.
Scheme 19: Asymmetric α-oxygenation and α-amination of carbonyls reported by Wirth et al.
Scheme 20: Asymmetric α-functionalization of ketophenols using chiral quaternary ammonium (hypo)iodite salt re...
Scheme 21: Oxidative Intramolecular coupling by Gong et al.
Scheme 22: α-Sulfonyl and α-phosphoryl oxylation of ketones reported by Masson et al.
Scheme 23: α-Fluorination of β-keto esters.
Scheme 24: Alkynylation of β-ketoesters and amides catalyzed by phase-transfer catalyst.
Scheme 25: Alkynylation of β-ketoesters and dearomative alkynylation of phenols.
Beilstein J. Org. Chem. 2018, 14, 1021–1027, doi:10.3762/bjoc.14.88
Graphical Abstract
Figure 1: Selected examples of bioactive compounds containing the 2-oxazoline motif.
Figure 2: The catalytic difluorination of alkenes (top) and the proposed fluorocyclisation via the same I(I)/...
Figure 3: Substrate scope. aReaction conducted on 1 mmol scale. bReaction time increased to 40 hours. cReacti...
Scheme 1: Exploring diastereocontrol and the synthesis of the fluorohydrin 3. Yields in parentheses were dete...
Figure 4: X-ray molecular structure of compound 2c. Thermal ellipsoids shown at the 50% propability level. To...
Beilstein J. Org. Chem. 2018, 14, 856–860, doi:10.3762/bjoc.14.71
Graphical Abstract
Figure 1: Four possible isomers reachable through the presented approach.
Scheme 1: Sharpless epoxidation to gain D-galacto- 5a and L-galacto-configured epoxythreitol 5b.
Scheme 2: Reagents and conditions: a) i) (COCl)2, DMSO, Et3N, DCM, ii) triethyl phosphonoacetate, NaH, DCM; b...
Scheme 3: Proposed mechanism of the Pd-catalyzed azide substitution of 6a in protic solvent.
Scheme 4: Approach towards peracetylated D-IdoNAc 2c, reactions and conditions: a) Ti(OiPr)4, t-BuOOH, D-DET,...
Beilstein J. Org. Chem. 2018, 14, 849–855, doi:10.3762/bjoc.14.70
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. 2017, 13, 2764–2799, doi:10.3762/bjoc.13.272
Graphical Abstract
Scheme 1: Trifluoromethylation of enol acetates by Langlois.
Scheme 2: Trifluoromethylation of (het)aryl enol acetates.
Scheme 3: Mechanism for the trifluoromethylation of enol acetates.
Scheme 4: Oxidative trifluoromethylation of unactivated olefins and mechanistic pathway.
Scheme 5: Oxidative trifluoromethylation of acetylenic substrates.
Scheme 6: Metal free trifluoromethylation of styrenes.
Scheme 7: Synthesis of α-trifluoromethylated ketones by oxytrifluoromethylation of heteroatom-functionalised ...
Scheme 8: Catalysed photoredox trifluoromethylation of vinyl azides.
Scheme 9: Oxidative difunctionalisation of alkenyl MIDA boronates.
Scheme 10: Synthesis of β-trifluoromethyl ketones from cyclopropanols.
Scheme 11: Aryltrifluoromethylation of allylic alcohols.
Scheme 12: Cascade multicomponent synthesis of nitrogen heterocycles via azotrifluoromethylation of alkenes.
Scheme 13: Photocatalytic azotrifluoromethylation of alkenes with aryldiazonium salts and CF3SO2Na.
Scheme 14: Copper-promoted intramolecular aminotrifluoromethylation of alkenes with CF3SO2Na.
Scheme 15: Oxytrifluoromethylation of alkenes with CF3SO2Na and hydroxamic acid.
Scheme 16: Manganese-catalysed oxytrifluoromethylation of styrene derivatives.
Scheme 17: Oxytrifluoromethylation of alkenes with NMP/O2 and CF3SO2Na.
Scheme 18: Intramolecular oxytrifluoromethylation of alkenes.
Scheme 19: Hydrotrifluoromethylation of styrenyl alkenes and unactivated aliphatic alkenes.
Scheme 20: Hydrotrifluoromethylation of electron-deficient alkenes.
Scheme 21: Hydrotrifluoromethylation of alkenes by iridium photoredox catalysis.
Scheme 22: Iodo- and bromotrifluoromethylation of alkenes by CF3SO2Na/I2O5 or CF3SO2Na / NaBrO3.
Scheme 23: N-methyl-9-mesityl acridinium and visible-light-induced chloro-, bromo- and SCF3 trifluoromethylati...
Scheme 24: Carbotrifluoromethylation of N-arylacrylamides with CF3SO2Na / TBHP by Lipshutz.
Scheme 25: Carbotrifluoromethylation of N-arylacrylamides with CF3SO2Na/TBHP reported by Lei.
Scheme 26: Carbotrifluoromethylation of N-arylacrylamides with CF3SO2Na/(NH4)2S2O8.
Scheme 27: Metal-free carbotrifluoromethylation of N-arylacrylamides with CF3SO2Na/K2S2O8 reported by Wang.
Scheme 28: Metal-free carbotrifluoromethylation of N-arylacrylamides with CF3SO2Na/PIDA reported by Fu.
Scheme 29: Metal-free cascade trifluoromethylation/cyclisation of N-arylmethacrylamides (a) and enynes (b) wit...
Scheme 30: Trifluoromethylation/cyclisation of N-arylcinnamamides: Synthesis of 3,4-disubstituted dihydroquino...
Scheme 31: Trifluoromethylation/cyclisation of aromatic-containing unsaturated ketones.
Scheme 32: Chemo- and regioselective cascade trifluoromethylation/heteroaryl ipso-migration of unactivated alk...
Scheme 33: Copper-mediated 1,2-bis(trifluoromethylation) of alkenes.
Scheme 34: Trifluoromethylation of aromatics with CF3SO2Na reported by Langlois.
Scheme 35: Baran’s oxidative C–H trifluoromethylation of heterocycles.
Scheme 36: Trifluoromethylation of acetanilides and anilines.
Scheme 37: Trifluoromethylation of heterocycles in water.
Scheme 38: Trifluoromethylation of coumarins in a continuous-flow reactor.
Scheme 39: Oxidative trifluoromethylation of coumarins, quinolines and pyrimidinones.
Scheme 40: Oxidative trifluoromethylation of pyrimidinones and pyridinones.
Scheme 41: Phosphovanadomolybdic acid-catalysed direct C−H trifluoromethylation.
Scheme 42: Oxidative trifluoromethylation of imidazopyridines and imidazoheterocycles.
Scheme 43: Oxidative trifluoromethylation of imidazoheterocycles and imidazoles in ionic liquid/water.
Scheme 44: Oxidative trifluoromethylation of 8-aminoquinolines.
Scheme 45: Oxidative trifluoromethylation of various 8-aminoquinolines using the supported catalyst CS@Cu(OAc)2...
Scheme 46: Oxidative trifluoromethylation of the naphthylamide 70.
Scheme 47: Oxidative trifluoromethylation of various arenes in the presence of CF3SO2Na and sodium persulfate.
Scheme 48: Trifluoromethylation of electron-rich arenes and unsymmetrical biaryls with CF3SO2Na in the presenc...
Figure 1: Trifluoromethylated coumarin and flavone.
Scheme 49: Metal-free trifluoromethylation catalysed by a photoredox organocatalyst.
Scheme 50: Quinone-mediated trifluoromethylation of arenes and heteroarenes.
Scheme 51: Metal- and oxidant-free photochemical trifluoromethylation of arenes.
Scheme 52: Copper-mediated trifluoromethylation of arenediazonium tetrafluoroborates.
Scheme 53: Oxidative trifluoromethylation of aryl- and heteroarylboronic acids.
Scheme 54: Oxidative trifluoromethylation of aryl- and vinylboronic acids.
Scheme 55: Oxidative trifluoromethylation of unsaturated potassium organotrifluoroborates.
Scheme 56: Oxidative trifluoromethylation of (hetero)aryl- and vinyltrifluoroborates.
Scheme 57: Copper−catalysed decarboxylative trifluoromethylation of cinnamic acids.
Scheme 58: Iron-mediated decarboxylative trifluoromethylation of α,β-unsaturated carboxylic acids.
Scheme 59: Cu/Ag-catalysed decarboxylative trifluoromethylation of cinnamic acids.
Scheme 60: I2O5-Promoted decarboxylative trifluoromethylation of cinnamic acids.
Scheme 61: Silver(I)-catalysed denitrative trifluoromethylation of β-nitrostyrenes.
Scheme 62: Copper-catalysed direct trifluoromethylation of styrene derivatives.
Scheme 63: Transition-metal-free synthesis of β-trifluoromethylated enamines.
Scheme 64: I2O5-mediated iodotrifluoromethylation of alkynes.
Scheme 65: Silver-catalysed tandem trifluoromethylation/cyclisation of aryl isonitriles.
Scheme 66: Photoredox trifluoromethylation of 2-isocyanobiphenyls.
Scheme 67: Trifluoromethylation of potassium alkynyltrifluoroborates with CF3SO2Na.
Scheme 68: N-trifluoromethylation of nitrosoarenes with CF3SO2Na (SQ: semiquinone).
Scheme 69: Trifluoromethylation of disulfides with CF3SO2Na.
Scheme 70: Trifluoromethylation of thiols with CF3SO2Na/I2O5.
Scheme 71: Electrophilic trifluoromethylsulfenylation by means of CF3SO2Na/(EtO)2P(O)H/CuCl/DMSO.
Scheme 72: Electrophilic trifluoromethylsulfenylation by means of CF3SO2Na/(EtO)2P(O)H/TMSCl.
Scheme 73: Electrophilic trifluoromethylsulfenylation by means of CF3SO2Na/PPh3/N-chlorophthalimide.
Scheme 74: Electrophilic trifluoromethylsulfenylation by means of CF3SO2Na/PCl3.
Scheme 75: Electrophilic trifluoromethylsulfenylation by means of CF3SO2Na/PCl3.
Scheme 76: Trifluoromethylsulfenylation of aryl iodides with in situ generated CuSCF3 (DMI: 1,3-dimethyl-2-imi...
Scheme 77: Pioneering trifluoromethylsulfinylation of N, O, and C-nucleophiles.
Scheme 78: Trifluoromethylsulfinylation of (1R,2S)-ephedrine (Im: imidazole; DIEA: N,N-diisopropylethylamine).
Scheme 79: Trifluoromethylsulfinylation of substituted benzenes with CF3SO2Na/CF3SO3H.
Scheme 80: Trifluoromethylsulfinylation of indoles with CF3SO2Na/P(O)Cl3.
Scheme 81: Trifluoromethylsulfinylation of indoles with CF3SO2Na/PCl3.
Scheme 82: Formation of triflones from benzyl bromides (DMA: dimethylacetamide).
Scheme 83: Formation of α-trifluoromethylsulfonyl ketones, esters, and amides.
Scheme 84: Allylic trifluoromethanesulfonylation of aromatic allylic alcohols.
Scheme 85: Copper-catalysed couplings of aryl iodonium salts with CF3SO2Na.
Scheme 86: Palladium-catalysed trifluoromethanesulfonylation of aryl triflates and chlorides with CF3SO2Na.
Scheme 87: Copper-catalysed coupling of arenediazonium tetrafluoroborates with CF3SO2Na.
Scheme 88: Synthesis of phenyltriflone via coupling of benzyne with CF3SO2Na.
Scheme 89: Synthesis of 1-trifluoromethanesulfonylcyclopentenes from 1-alkynyl-λ3-bromanes and CF3SO2Na.
Scheme 90: One-pot synthesis of functionalised vinyl triflones.
Scheme 91: Regioselective synthesis of vinyltriflones from styrenes.
Scheme 92: Trifluoromethanesulfonylation of alkynyl(phenyl) iodonium tosylates by CF3SO2Na.
Scheme 93: Synthesis of thio- and selenotrifluoromethanesulfonates.
Beilstein J. Org. Chem. 2017, 13, 2710–2738, doi:10.3762/bjoc.13.269
Graphical Abstract
Scheme 1: Generation of phosphorus ylides from vinylphosphonium salts.
Scheme 2: Intramolecular Wittig reaction with the use of vinylphosphonium salts.
Scheme 3: Alkylation of diphenylvinylphosphine with methyl or benzyl iodide.
Scheme 4: Methylation of isopropenyldiphenylphosphine with methyl iodide.
Scheme 5: Alkylation of phosphines with allyl halide derivatives and subsequent isomerization of intermediate...
Scheme 6: Alkylation of triphenylphosphine with vinyl triflates in the presence of (Ph3P)4Pd.
Scheme 7: Mechanism of alkylation of triphenylphosphine with vinyl triflates in the presence of (Ph3P)4Pd as ...
Scheme 8: β-Elimination of phenol from β-phenoxyethyltriphenylphosphonium bromide.
Scheme 9: β-Elimination of phenol from β-phenoxyethylphosphonium salts in an alkaline environment.
Scheme 10: Synthesis and subsequent dehydrohalogenation of α-bromoethylphosphonium bromide.
Scheme 11: Synthesis of tributylvinylphosphonium iodides via Peterson-type olefination of α-trimethylsilylphos...
Scheme 12: Synthesis of 1-cycloalkenetriphenylphosphonium salts by electrochemical oxidation of triphenylphosp...
Scheme 13: Suggested mechanism for the electrochemical synthesis of 1-cycloalkenetriphenylphosphonium salts.
Scheme 14: Generation of α,β-(dialkoxycarbonyl)vinylphosphonium salts by addition of triphenylphosphine to ace...
Scheme 15: Synthesis of 2-(N-acylamino)vinylphosphonium halides by imidoylation of β-carbonyl ylides with imid...
Scheme 16: Imidoylation of β-carbonyl ylides with imidoyl halides generated in situ.
Scheme 17: Synthesis of 2-benzoyloxyvinylphosphonium bromide from 2-propynyltriphenylphosphonium bromide.
Scheme 18: Synthesis of 2-aminovinylphosphonium salts via nucleophilic addition of amines to 2-propynyltriphen...
Scheme 19: Deacylation of 2-(N-acylamino)vinylphosphonium chlorides to 2-aminovinylphosphonium salts.
Scheme 20: Resonance structures of 2-aminovinylphosphonium salts and tautomeric equilibrium between aminovinyl...
Scheme 21: Synthesis of 2-aminovinylphosphonium salts by reaction of (formylmethyl)triphenylphosphonium chlori...
Scheme 22: Generation of ylides by reaction of vinyltriphenylphosphonium bromide with nucleophiles and their s...
Scheme 23: Intermolecular Wittig reaction with the use of vinylphosphonium bromide and organocopper compounds ...
Scheme 24: Intermolecular Wittig reaction with the use of ylides generated from vinylphosphonium bromides and ...
Scheme 25: Direct transformation of vinylphosphonium salts into ylides in the presence of potassium tert-butox...
Scheme 26: A general method for synthesis of carbo- and heterocyclic systems by the intramolecular Wittig reac...
Scheme 27: Synthesis of 2H-chromene by reaction of vinyltriphenylphosphonium bromide with sodium 2-formylpheno...
Scheme 28: Synthesis of 2,5-dihydro-2,3-dimethylfuran by reaction of vinylphosphonium bromide with 3-hydroxy-2...
Scheme 29: Synthesis of 2H-chromene and 2,5-dihydrofuran derivatives in the intramolecular Wittig reaction wit...
Scheme 30: Enantioselective synthesis of 3,6-dihydropyran derivatives from vinylphosphonium bromide and enanti...
Scheme 31: Synthesis of 2,5-dihydrothiophene derivatives in the intramolecular Wittig reaction from vinylphosp...
Scheme 32: Synthesis of bicyclic pyrrole derivatives in the reaction of vinylphosphonium halides and 2-pyrrolo...
Scheme 33: Stereoselective synthesis of bicyclic 2-pyrrolidinone derivatives in the reaction of vinylphosphoni...
Scheme 34: Stereoselective synthesis of 3-pyrroline derivatives in the intramolecular Wittig reaction from vin...
Scheme 35: Synthesis of cyclic alkenes in the intramolecular Wittig reaction from vinylphosphonium bromide and...
Scheme 36: Synthesis of 1,3-cyclohexadienes by reaction of 1,3-butadienyltriphenylphosphonium bromide with eno...
Scheme 37: Synthesis of bicyclo[3.3.0]octenes by reaction of vinylphosphonium salts with cyclic diketoester.
Scheme 38: Synthesis of quinoline derivatives in the intramolecular Wittig reaction from 2-(2-acylphenylamino)...
Scheme 39: Stereoselective synthesis of γ-aminobutyric acid in the intermolecular Wittig reaction from chiral ...
Scheme 40: Synthesis of allylamines in the intermolecular Wittig reaction from 2-aminovinylphosphonium bromide...
Scheme 41: A general route towards α,β-di(alkoxycarbonyl)vinylphosphonium salts and their subsequent possible ...
Scheme 42: Generation of resonance-stabilized phosphorus ylides via the reaction of triphenylphosphine with di...
Scheme 43: Synthesis of resonance-stabilized phosphorus ylides in the reaction of triphenylphosphine, dialkyl ...
Scheme 44: Synthesis of resonance-stabilized phosphorus ylides via the reaction of triphenylphosphine with dia...
Scheme 45: Generation of resonance-stabilized phosphorus ylides in the reaction of acetylenedicarboxylate, tri...
Scheme 46: Synthesis of resonance-stabilized phosphorus ylides via the reaction of dialkyl acetylenedicarboxyl...
Scheme 47: Synthesis of resonance-stabilized ylides derived from semicarbazones, aromatic amides, and 3-(aryls...
Scheme 48: Synthesis of resonance-stabilized ylides via the reaction of triphenylphosphine with dialkyl acetyl...
Scheme 49: Synthesis of resonance-stabilized ylides in the reaction of triphenylphosphine, dialkyl acetylenedi...
Scheme 50: Synthesis of N-acylated α,β-unsaturated γ-lactams via resonance-stabilized phosphorus ylides derive...
Scheme 51: Synthesis of resonance-stabilized phosphorus ylides derived from 6-amino-N,N'-dimethyluracil and th...
Scheme 52: Generation of resonance-stabilized phosphorus ylides in the reaction of triphenylphosphine, dialkyl...
Scheme 53: Synthesis of resonance-stabilized phosphorus ylides via the reaction of triphenylphosphine with dia...
Scheme 54: Synthesis of 1,3-dienes via intramolecular Wittig reaction with the use of resonance-stabilized yli...
Scheme 55: Synthesis of 1,3-dienes in the intramolecular Wittig reaction from ylides generated from dimethyl a...
Scheme 56: Synthesis of 4-(2-quinolyl)cyclobutene-1,2,3-tricarboxylic acid triesters and isomeric cyclopenteno...
Scheme 57: Synthesis of 4-arylquinolines via resonance-stabilized ylides in the intramolecular Wittig reaction....
Scheme 58: Synthesis of furan derivatives via resonance-stabilized ylides in the intramolecular Wittig reactio...
Scheme 59: Synthesis of 1,3-indanedione derivatives via resonance-stabilized ylides in the intermolecular Witt...
Scheme 60: Synthesis of coumarin derivatives via nucleophilic displacement of the triphenylphosphonium group i...
Scheme 61: Synthesis of 6-formylcoumarin derivatives and their application in the synthesis of dyads.
Scheme 62: Synthesis of di- and tricyclic coumarin derivatives in the reaction of pyrocatechol with two vinylp...
Scheme 63: Synthesis of mono-, di-, and tricyclic derivatives in the reaction of pyrogallol with one or two vi...
Scheme 64: Synthesis of 1,4-benzoxazine derivative by nucleophilic displacement of the triphenylphosphonium gr...
Scheme 65: Synthesis of 7-oxo-7H-pyrido[1,2,3-cd]perimidine derivative via nucleophilic displacement of the tr...
Scheme 66: Application of vinylphosphonium salts in the Diels–Alder reaction with dienes.
Scheme 67: Synthesis of pyrroline derivatives from vinylphosphonium bromide and 5-(4H)-oxazolones.
Scheme 68: Synthesis of pyrrole derivatives in the reactions of vinyltriphenylphosphonium bromide with protona...
Scheme 69: Synthesis of dialkyl 2-(alkylamino)-5-aryl-3,4-furanedicarboxylates via intermediate α,β-di(alkoxyc...
Scheme 70: Synthesis of 1,4-benzoxazine derivatives from acetylenedicarboxylates, phosphines, and 1-nitroso-2-...
Beilstein J. Org. Chem. 2017, 13, 2186–2213, doi:10.3762/bjoc.13.219
Graphical Abstract
Figure 1: Summary of the synthetic routes to prepare phosphonic acids detailed in this review. The numbers in...
Figure 2: Chemical structure of dialkyl phosphonate, phosphonic acid and illustration of the simplest phospho...
Figure 3: Illustration of some phosphonic acid exhibiting bioactive properties. A) Phosphonic acids for biome...
Figure 4: Illustration of the use of phosphonic acids for their coordination properties and their ability to ...
Figure 5: Hydrolysis of dialkyl phosphonate to phosphonic acid under acidic conditions.
Figure 6: Examples of phosphonic acids prepared by hydrolysis of dialkylphosphonate with HCl 35% at reflux (16...
Figure 7: A) and B) Observation of P–C bond breaking during the hydrolysis of phosphonate with concentrated H...
Figure 8: Mechanism of the hydrolysis of dialkyl phosphonate with HCl in water.
Figure 9: Hydrolysis of bis-tert-butyl phosphonate 28 into phosphonic acid 29 [137].
Figure 10: A) Hydrolysis of diphenyl phosphonate into phosphonic acid in acidic media. B) Examples of phosphon...
Figure 11: Suggested mechanism occurring for the first step of the hydrolysis of diphenyl phosphonate into pho...
Figure 12: A) Hydrogenolysis of dibenzyl phosphonate to phosphonic acid. B) Compounds 33, 34 and 35 were prepa...
Figure 13: A) Preparation of phosphonic acid from diphenyl phosphonate with the Adam’s catalyst. B) Compounds ...
Figure 14: Suggested mechanism for the preparation of phosphonic acid from dialkyl phosphonate using bromotrim...
Figure 15: A) Reaction of the phosphonate-thiophosphonate 37 with iodotrimethylsilane followed by methanolysis...
Figure 16: Synthesis of hydroxymethylenebisphosphonic acid by reaction of tris(trimethylsilyl) phosphite with ...
Figure 17: Synthesis of the phosphonic acid disodium salt 48 by reaction of mono-hydrolysed phosphonate 47 wit...
Figure 18: Phosphonic acid synthesized by the sequence 1) bromotrimethylsilane 2) methanolysis or hydrolysis. ...
Figure 19: Polyphosphonic acids and macromolecular compounds prepared by the hydrolysis of dialkyl phosphonate...
Figure 20: Examples of organometallic complexes functionalized with phosphonic acids that were prepared by the...
Figure 21: Side reaction observed during the hydrolysis of methacrylate monomer functionalized with phosphonic...
Figure 22: Influence of the reaction time during the hydrolysis of compound 76.
Figure 23: Dealkylation of dialkyl phosphonates with boron tribromide.
Figure 24: Dealkylation of diethylphosphonate 81 with TMS-OTf.
Figure 25: Synthesis of substituted phenylphosphonic acid 85 from the phenyldichlorophosphine 83.
Figure 26: Hydrolysis of substituted phenyldichlorophosphine oxide 86 under basic conditions.
Figure 27: A) Illustration of the synthesis of chiral phosphonic acids from phosphonodiamides. B) Examples of ...
Figure 28: A) Illustration of the synthesis of the phosphonic acid 98 from phosphonodiamide 97. B) Use of cycl...
Figure 29: Synthesis of tris(phosphonophenyl)phosphine 109.
Figure 30: Moedritzer–Irani reaction starting from A) primary amine or B) secondary amine. C) Examples of phos...
Figure 31: Phosphonic acid-functionalized polymers prepared by Moedritzer–Irani reaction.
Figure 32: Reaction of phosphorous acid with imine in the absence of solvent.
Figure 33: A) Reaction of phosphorous acid with nitrile and examples of aminomethylene bis-phosphonic acids. B...
Figure 34: Reaction of carboxylic acid with phosphorous acid and examples of compounds prepared by this way.
Figure 35: Synthesis of phosphonic acid by oxidation of phosphinic acid (also identified as phosphonous acid).
Figure 36: Selection of reaction conditions to prepare phosphonic acids from phosphinic acids.
Figure 37: Synthesis of phosphonic acid from carboxylic acid and white phosphorus.
Figure 38: Synthesis of benzylphosphonic acid 136 from benzaldehyde and red phosphorus.
Figure 39: Synthesis of graphene phosphonic acid 137 from graphite and red phosphorus.