5th International Symposium on Synthesis and Catalysis (ISySyCat2023)
- Anthony J. Burke and
- Elisabete P. Carreiro
Beilstein J. Org. Chem. 2024, 20, 2704–2707, doi:10.3762/bjoc.20.227
Synthesis of benzo[f]quinazoline-1,3(2H,4H)-diones
- Ruben Manuel Figueira de Abreu,
- Peter Ehlers and
- Peter Langer
Beilstein J. Org. Chem. 2024, 20, 2708–2719, doi:10.3762/bjoc.20.228
Graphical Abstract
Figure 1: Synthesis of uracil-based alkynes and aryl structures [51,62-65].
Figure 2: Structures of uracil derivatives A, B, and C.
Scheme 1: Strategy for the synthesis of the cyclised product 5. Conditions: i) Br2 (2 equiv), Ac2O (1.5 equiv...
Scheme 2: Synthesis and isolated yields of 1,3-dimethyl-5-aryl-6-[2-(aryl)ethynyl]uracils 4a–i. Reaction cond...
Scheme 3: Scope and isolated yields of the synthesis of 5. Reaction conditions: 4 (1 equiv), p-TsOH·H2O (20 e...
Scheme 4: Proposed reaction mechanism of the cyclisation with N,N-dimethylanilino functional groups.
Figure 3: UV–vis absorption (left) and emission (right, λex = 400 nm) spectra of 5a, 5d, 5f, 5g, 5h, and 5i i...
Young investigators in natural products chemistry, biosynthesis, and enzymology
- Jeffrey D. Rudolf,
- Lena Barra and
- Takayoshi Awakawa
Beilstein J. Org. Chem. 2024, 20, 2720–2721, doi:10.3762/bjoc.20.229
Synthesis of spiroindolenines through a one-pot multistep process mediated by visible light
- Francesco Gambuti,
- Jacopo Pizzorno,
- Chiara Lambruschini,
- Renata Riva and
- Lisa Moni
Beilstein J. Org. Chem. 2024, 20, 2722–2731, doi:10.3762/bjoc.20.230
Graphical Abstract
Figure 1: Selected natural products containing spiro-indolenines.
Scheme 1: Synthesis of spiro[indole-heterocycles].
Scheme 2: Synthetic strategy for the new synthesis of 2,3-diaminoindolenines [21] and spiro[indole-isoquinolines]....
Scheme 3: Scope of the synthesis of spiro[indole-THIQs]. aα-aminoamidine 2b has been isolated (54%) too; bα-a...
Scheme 4: Two-step synthesis using p-methylaniline.
Scheme 5: Investigation of the one-pot four-step synthetic protocol employing N-Ph-benzoxazepine 5.
Figure 2: Time profile of the reaction of N-Ph-THIQ, 3,5-dimethoxyaniline and t-BuNC conducted under optimize...
Scheme 6: Proposed mechanism.
Interaction of a pyrene derivative with cationic [60]fullerene in phospholipid membranes and its effects on photodynamic actions
- Hayato Takagi,
- Çetin Çelik,
- Ryosuke Fukuda,
- Qi Guo,
- Tomohiro Higashino,
- Hiroshi Imahori,
- Yoko Yamakoshi and
- Tatsuya Murakami
Beilstein J. Org. Chem. 2024, 20, 2732–2738, doi:10.3762/bjoc.20.231
Graphical Abstract
Figure 1: (a) Chemical structure and schematic illustration of the charge-separated state of a triad molecule...
Figure 2: Differential scanning calorimetry analysis for the phase transition of liposomes (1 mM phospholipid...
Figure 3: UV–vis absorption spectra of liposomes (1 mM phospholipid) with C60 (a) or a cationic derivative of...
Figure 4: Fluorescence spectra of 1-pyrenebutyric acid (PyBA) in cationic derivative of C60 (catC60)-loaded l...
Figure 5: Photoinduced generation of reactive oxygen species (ROS) by cationic derivative of C60 (catC60)-loa...
Copper-catalyzed yne-allylic substitutions: concept and recent developments
- Shuang Yang and
- Xinqiang Fang
Beilstein J. Org. Chem. 2024, 20, 2739–2775, doi:10.3762/bjoc.20.232
Graphical Abstract
Scheme 1: Copper-catalyzed allylic and yne-allylic substitution.
Scheme 2: Challenges in achieving highly selective yne-allylic substitution.
Scheme 3: Yne-allylic substitutions using indoles and pyroles.
Scheme 4: Yne-allylic substitutions using amines.
Scheme 5: Yne-allylic substitution using 1,3-dicarbonyls.
Scheme 6: Postulated mechanism via copper acetylide-bonded allylic cation.
Scheme 7: Amine-participated asymmetric yne-allylic substitution.
Scheme 8: Asymmetric decarboxylative yne-allylic substitution.
Scheme 9: Asymmetric yne-allylic alkoxylation and alkylation.
Scheme 10: Proposed mechanism for Cu(I) system.
Scheme 11: Asymmetric yne-allylic dialkylamination.
Scheme 12: Proposed mechanism of yne-allylic dialkylamination.
Scheme 13: Asymmetric yne-allylic sulfonylation.
Scheme 14: Proposed mechanism of yne-allylic sulfonylation.
Scheme 15: Aymmetric yne-allylic substitutions using indoles and indolizines.
Scheme 16: Double yne-allylic substitutions using pyrrole.
Scheme 17: Proposed mechanism of yne-allylic substitution using electron-rich arenes.
Scheme 18: Aymmetric yne-allylic monofluoroalkylations.
Scheme 19: Proposed mechanism.
Scheme 20: Aymmetric yne-allylic substitution of yne-allylic esters with anthrones.
Scheme 21: Aymmetric yne-allylic substitution of yne-allylic esters with coumarins.
Scheme 22: Aymmetric yne-allylic substitution of with coumarins by Lin.
Scheme 23: Proposed mechanism.
Scheme 24: Amination by alkynylcopper driven dearomatization and rearomatization.
Scheme 25: Arylation by alkynylcopper driven dearomatization and rearomatization.
Scheme 26: Remote substitution/cyclization/1,5-H shift process.
Scheme 27: Proposed mechanism.
Scheme 28: Arylation or amination by alkynylcopper driven dearomatization and rearomatization.
Scheme 29: Remote nucleophilic substitution of 5-ethynylthiophene esters.
Scheme 30: Proposed mechanism.
Scheme 31: [4 + 1] annulation of yne-allylic esters and cyclic 1,3-dicarbonyls.
Scheme 32: Asymmetric [4 + 1] annulation of yne-allylic esters.
Scheme 33: Proposed mechanism.
Scheme 34: Asymmetric [3 + 2] annulation of yne-allylic esters.
Scheme 35: Postulated annulation step.
Scheme 36: [4 + 1] Annulations of vinyl ethynylethylene carbonates and 1,3-dicarbonyls.
Scheme 37: Proposed mechanism.
Scheme 38: Formal [4 + 1] annulations with amines.
Scheme 39: Formal [4 + 2] annulations with hydrazines.
Scheme 40: Proposed mechanism.
Scheme 41: Dearomative annulation of 1-naphthols and yne-allylic esters.
Scheme 42: Dearomative annulation of phenols or 2-naphthols and yne-allylic esters.
Scheme 43: Postulated annulation mechanism.
Scheme 44: Dearomative annulation of phenols or 2-naphthols.
Scheme 45: Dearomative annulation of indoles.
Scheme 46: Postulated annulation step.
Scheme 47: Asymmetric [4 + 1] cyclization of yne-allylic esters with pyrazolones.
Scheme 48: Proposed mechanism.
Scheme 49: Construction of C–C axially chiral arylpyrroles.
Scheme 50: Construction of C–N axially chiral arylpyrroles.
Scheme 51: Construction of chiral arylpyrroles with 1,2-di-axial chirality.
Scheme 52: Proposed mechanism.
Scheme 53: CO2 shuttling in yne-allylic substitution.
Scheme 54: CO2 fixing in yne-allylic substitution.
Scheme 55: Proposed mechanism.
Access to optically active tetrafluoroethylenated amines based on [1,3]-proton shift reaction
- Yuta Kabumoto,
- Eiichiro Yoshimoto,
- Bing Xiaohuan,
- Masato Morita,
- Motohiro Yasui,
- Shigeyuki Yamada and
- Tsutomu Konno
Beilstein J. Org. Chem. 2024, 20, 2776–2783, doi:10.3762/bjoc.20.233
Graphical Abstract
Figure 1: Various applications of tetrafluoroethylenated molecules.
Scheme 1: Precedent synthetic approaches to optically active compounds possessing a tetrafluoroethylene group...
Scheme 2: Synthetic strategy for preparing fluorine-containing amines via [1,3]-proton shift reactions.
Scheme 3: Preparation of the substrates used in this study.
Scheme 4: Derivatization of (S)-20b to (S)-23b for determining the optical purity of (S)-20b.
Scheme 5: Substrate scope for the present [1,3]-proton shift reaction. aYields are determined by 19F NMR spec...
Scheme 6: Proposed reaction mechanism.
C–C Coupling in sterically demanding porphyrin environments
- Liam Cribbin,
- Brendan Twamley,
- Nicolae Buga,
- John E. O’ Brien,
- Raphael Bühler,
- Roland A. Fischer and
- Mathias O. Senge
Beilstein J. Org. Chem. 2024, 20, 2784–2798, doi:10.3762/bjoc.20.234
Graphical Abstract
Figure 1: (A) Structures of tetrasubstituted 5,10,15,20-tetraphenylporphyrin (TPP, 1), dodecasubstituted 2,3,...
Scheme 1: Reaction scheme for the synthesis of OET-xBrPPs and subsequent Ni(II) metalation.
Figure 2: Substrates used for the investigations for the Suzuki–Miyaura coupling reactions.
Scheme 2: Scope of arm-extended dodecasubstituted porphyrins synthesized via modification of the meso-para-ph...
Scheme 3: Scope of arm-extended dodecasubstituted porphyrins synthesized via reaction at the meso-meta-phenyl...
Scheme 4: Attempts of arm-extension of dodecasubstituted porphyrins at the meso-ortho-phenyl position.
Scheme 5: Borylation and subsequent Suzuki–Miyaura coupling of porphyrin 13.
Figure 3: View of the molecular structure of compounds 26 (top left) and 27 (top right) with atomic displacem...
Figure 4: Left: packing diagram of 27 viewed normal to the c-axis showing the channels in the lattice with th...
Figure 5: Left: view of part 0 2 in the molecular structure of the α2β2-atropisomer, 11 in the crystal, hydro...
Figure 6: Schematic representation of porphyrin 37 showing a doubly intercalated structure.
Mechanochemical difluoromethylations of ketones
- Jinbo Ke,
- Pit van Bonn and
- Carsten Bolm
Beilstein J. Org. Chem. 2024, 20, 2799–2805, doi:10.3762/bjoc.20.235
Graphical Abstract
Scheme 1: Overview over difluoromethyl enol ether syntheses from acyclic and cyclic 1,3-diones (A), acyclic k...
Scheme 2: Attempted difluoromethylation of 1a in solution. The reactions were performed on a 0.2 mmol scale. ...
Scheme 3: Scope of ketones. The yields were determined by 1H NMR spectroscopy using 1,2-dichloroethane as the...
Scheme 4: Proposed mechanism (A) and mechanistic investigations (B and C). The yields were determined by 1H N...
Synthesis and antimycotic activity of new derivatives of imidazo[1,2-a]pyrimidines
- Dmitriy Yu. Vandyshev,
- Daria A. Mangusheva,
- Khidmet S. Shikhaliev,
- Kirill A. Scherbakov,
- Oleg N. Burov,
- Alexander D. Zagrebaev,
- Tatiana N. Khmelevskaya,
- Alexey S. Trenin and
- Fedor I. Zubkov
Beilstein J. Org. Chem. 2024, 20, 2806–2817, doi:10.3762/bjoc.20.236
Graphical Abstract
Figure 1: Some biologically active compounds and organic fluorophores containing the imidazo[1,2-a]pyrimidine...
Figure 2: Existing approaches to imidazo[1,2-a]pyrimidines.
Scheme 1: Reaction of 2-aminoimidazole (1) with N-substituted maleimides (2) and N-arylitaconimides (3).
Scheme 2: Plausible synthetic routes for the interaction of N-substituted maleimides 2 with 2-aminoimidazole (...
Scheme 3: Plausible synthetic routes for the interaction of or N-arylitaconimides 3 with 2-aminoimidazole (1)....
Figure 3: Key correlations observed in the NOESY and HMBC spectra of the products 4d and 5d.
Scheme 4: Results of MEP calculations for the reaction of N-phenylmaleimide (2a) with 2-aminoimidazole (1).
Scheme 5: Results of MEP calculations for the reaction of N-phenylithaconimide (3a) with 2-aminoimidazole (1)....
Figure 4: Structures of imidazo[1,2-a]pyrimidines selected for docking and voriconazole selected for comparis...
Figure 5: (A) Position of the (S)-isomer of compound 4e in the active site of CYP51 after molecular dockinga....
Investigation of a bimetallic terbium(III)/copper(II) chemosensor for the detection of aqueous hydrogen sulfide
- Parvathy Mini,
- Michael R. Grace,
- Genevieve H. Dennison and
- Kellie L. Tuck
Beilstein J. Org. Chem. 2024, 20, 2818–2826, doi:10.3762/bjoc.20.237
Graphical Abstract
Figure 1: Previously reported lanthanide complexes [12,16,17].
Scheme 1: Synthesis of Tb.1.
Figure 2: Absorption (red line), excitation (yellow line, λem = 615 nm), and emission (green line, λex = 250 ...
Figure 3: (a) Changes in the luminescence emission spectrum of 5 µM [Tb.1·3Cu]3+ upon the addition of Na2S (0...
Figure 4: (a) Changes in the luminescence emission spectrum of 5 µM [Tb.1·3Cu]3+ upon the addition of Na2S (0...
Figure 5: Luminescence intensity of 5 μM Tb.1 in 10 mM Tris-HCl buffer, pH 7.4, containing 5% DMSO upon the a...
Figure 6: Changes in luminescent intensity of [Tb.1·3Cu]3+ (5 µM) detected at 545 nm in the presence of vario...
Figure 7: Chemical structure and mode of action of [Tb(DPA-N3)3]3− for detection of H2S(g) [11].
Synthesis of tricarbonylated propargylamine and conversion to 2,5-disubstituted oxazole-4-carboxylates
- Kento Iwai,
- Akari Hikasa,
- Kotaro Yoshioka,
- Shinki Tani,
- Kazuto Umezu and
- Nagatoshi Nishiwaki
Beilstein J. Org. Chem. 2024, 20, 2827–2833, doi:10.3762/bjoc.20.238
Graphical Abstract
Scheme 1: Synthesis of polyfunctionalized methane derivatives through successive nucleophilic additions to th...
Scheme 2: Cyclization of 4a quenched by D2O.
Scheme 3: Plausible mechanisms for the ring closure of 4.
Scheme 4: Hydration of the ethynyl group of 4a.
Multicomponent synthesis of α-branched amines using organozinc reagents generated from alkyl bromides
- Baptiste Leroux,
- Alexis Beaufils,
- Federico Banchini,
- Olivier Jackowski,
- Alejandro Perez-Luna,
- Fabrice Chemla,
- Marc Presset and
- Erwan Le Gall
Beilstein J. Org. Chem. 2024, 20, 2834–2839, doi:10.3762/bjoc.20.239
Graphical Abstract
Scheme 1: Scope of organozinc reagents. Yield was determined by titration with I2. Reaction conditions: Zn du...
Scheme 2: Scope of the reaction. Yield of isolated product is given.
N-Glycosides of indigo, indirubin, and isoindigo: blue, red, and yellow sugars and their cancerostatic activity
- Peter Langer
Beilstein J. Org. Chem. 2024, 20, 2840–2869, doi:10.3762/bjoc.20.240
Graphical Abstract
Scheme 1: Structures of indigo (1a), indirubin (2a) and isoindigo (3a).
Scheme 2: Structures of akashins A–C.
Scheme 3: Synthesis of 5b. Reagents and conditions: i) TMSOTf, 4 Å MS, CH2Cl2, −20 °C, 1.5 h, then 20 °C, 8–1...
Scheme 4: Synthesis of 7c. Reagents and conditions: i) TMSOTf, 4 Å MS, CH2Cl2, −18 °C, 3 h; then: TMSOTf, 4 Å...
Scheme 5: Synthesis of 1d. Reagents and conditions: i) chloroacetic acid, Na2CO3, reflux, 6 h; ii) Ac2O, NaOA...
Scheme 6: Synthesis of 10e. Reagents and conditions: i) p-TsOH·H2O, acetonitrile, MeOH, 1 d; ii) NIS, PPh3, D...
Scheme 7: Synthesis of akashins A–C. Reagents and conditions: i) TMSOTf, 4 Å MS, CH2Cl2, −18 to 20 °C, 15 h; ...
Scheme 8: Synthesis of 5d. Reagents and conditions: i) KMnO4, AcOH, high-power-stirring (12.000 rot/min), 20 ...
Scheme 9: Possible mechanism of the formation of 5c.
Scheme 10: Synthesis of 7d. Reagents and conditions: i) 1) CH2Cl2, 2) Me3SiI, 20 °C, 30 min, 3) 0 °C, 30 min, ...
Scheme 11: Synthesis of α-15b. Reagents and conditions: i) 1) CH2Cl2, 2) Me3SiI, 20 °C, 30 min, 3) 0 °C, 30 mi...
Scheme 12: Synthesis of isatin-N-glycosides 16a–f. Reagents and conditions: i) PhNH2, EtOH, 20 °C, 12 h; ii) Ac...
Scheme 13: Synthesis of 17–21. Reagents and conditions: i) Na2CO3, MeOH, 20 °C, 4 h.
Scheme 14: Synthesis of indirubin-N-glycosides α-17a and α-17b.
Scheme 15: Synthesis of β-17f. Reagents and conditions: i) 1) Na2CO3, MeOH, 20 °C, 4 h, 2) Ac2O/pyridine 1:1, ...
Scheme 16: Synthesis of β-24a. Reagents and conditions: i) n-PrOH, H2O, formic acid (buffer, 100 mM), 2 h, 65 ...
Scheme 17: Synthesis of isatin-N-glycosides 23b–g and 24b–g.
Scheme 18: Synthesis of β-29a,b. Reagents and conditions: i) EtOH, 20 °C, 12 h; ii) DDQ, dioxane, 20 °C, 12 h;...
Scheme 19: Synthesis of β-31a. Reagents and conditions: i) Na2SO3, dioxane, H2O, 110 °C, 2 d; ii) piperidine, ...
Scheme 20: Synthesis of 33a–d. Reagents and conditions: i) Ac2O, AcOH, NaOAc, 80 °C, 1 h; ii) 1) NaOMe, anhydr...
Scheme 21: Indirubins 34 and 35.
Scheme 22: Synthesis of 36f. Reagents and conditions: i) NaOH, H2O, 20 °C, 5 h; ii) HCl, NaNO2, H2O, −14 °C; i...
Scheme 23: Synthesis of 38a–h. Reagents and conditions: i) 1) 0.1 equiv NaOMe, MeOH, 20 °C, 15–20 min, 2) HOAc...
Scheme 24: Synthesis of 40a–h. Reagents and conditions: i) method A: EtOH/THF, cat. KOt-Bu, 20 °C, 3–4.5 h; me...
Scheme 25: Synthesis of 41a–d. Reagents and conditions: i) Ac2O, AcOH, NaOAc, 80 °C, 1 h.
Scheme 26: Synthesis of 41e. Reagents and conditions: i) AcOH, NaOAc, 110 °C, 24 h.
Scheme 27: Synthesis of E-β-43a–e and E-β-44a,b. Reagents and conditions: i) 1) NEt3, EtOH, 20 °C, 12 h, 2) DM...
Scheme 28: Synthesis of E-43f. Reagents and conditions: i) Na2CO3, MeOH, 20 °C, 6–24 h.
Scheme 29: Synthesis of 46a–m. Reagents and conditions: i) NEt3 (1 equiv), EtOH, 20 °C, 6–10 h; ii) MsCl, NEt3...
Scheme 30: Synthesis of 48a–d. Reagents and conditions: i) AcOH/Ac2O, NaOAc, 60 °C, 3–4 h.
Scheme 31: Synthesis of 48e. Reagents and conditions: i) NaOAc, AcOH, 110 °C, 24 h.
Scheme 32: Synthesis of β-49a,b. Reagents and conditions: i) AcOH/Ac2O, NaOAc, 60 °C, 3–4 h.
Scheme 33: Synthesis of β-54a,b. Reagents and conditions: i) 1) NaH, DMF, 0 °C, 15 min, 2) β-51a,b, 20 °C, 3 h...
Scheme 34: Synthesis of 54c–l. The yields refer to the yields of the first and second condensation step for ea...
Scheme 35: Synthesis of 57a–c and 58a–d. Reagents and conditions: i) HCl (conc.), AcOH, reflux, 24 h; ii) 1) B...
Scheme 36: Synthesis of 59a–e and 60a–e. Reagents and conditions: i) P(NEt2)3 (1.1 equiv), CH2Cl2, −78 °C to 2...
Scheme 37: Synthesis of 61a–d and 62a–d. Reagents and conditions: i) P(NEt2)3 (1.1 equiv), CH2Cl2, −78 °C to 2...
Scheme 38: Synthesis of β-64a–e and α-64a. Reagents and conditions: i) AcOH, Ac2O, NaOAc, 90 °C, 6 h.
Scheme 39: Synthesis of β-72a. Reagents and conditions: i) 66, EtOH, 20 °C, 12 h; ii) DDQ, dioxane, 20 °C, 12 ...
Scheme 40: Synthesis of β-72b.
Scheme 41: Synthesis of β-74a–c. Reagents and conditions: i) AcOH, Ac2O, NaOAc, 130 °C, 2 d.
Scheme 42: Synthesis of β-77. Reagents and conditions: i) 1) NEt3, EtOH, 20 °C, 12 h, 2) DMAP, NEt3, MsCl, 0 °...
Scheme 43: Synthesis of β-81a–f and β-80g. Reagents and conditions: i) AcOH, 80 °C, 1–3 h; ii) benzene, PTSA, ...
Scheme 44: Synthesis of 84a. Reagents and conditions: i) benzene, AlCl3, 20 °C, 10 min; ii) MeOH, NaOMe, 12 h,...
Scheme 45: Synthesis of 84b–l. The yields refer to the yields of the condensation and the deprotection step fo...
Synthesis of pyrrole-fused dibenzoxazepine/dibenzothiazepine/triazolobenzodiazepine derivatives via isocyanide-based multicomponent reactions
- Marzieh Norouzi,
- Mohammad Taghi Nazeri,
- Ahmad Shaabani and
- Behrouz Notash
Beilstein J. Org. Chem. 2024, 20, 2870–2882, doi:10.3762/bjoc.20.241
Graphical Abstract
Figure 1: Representation of distinguished structures of benzodiazepine/benzoxazepine/benzothiazepine with pha...
Scheme 1: Methods for the construction of pyrrole-fused heterocycles through I-MCR reactions.
Scheme 2: The model reaction of dibenzoxazepine, gem-diactivated olefin (2-benzylidenemalononitrile), and cyc...
Scheme 3: Substrate scope. Conditions: Reactions were carried out using 1 (0.55 mmol), 2 (0.55 mmol), and 3 (...
Scheme 4: Substrate scope..Conditions: reactions were carried out using 1 (0.55 mmol), 2 (0.55 mmol), and 5 (...
Figure 2: The crystal structure of 4h (CCDC 2365305).
Figure 3: The DNMR (dynamic nuclear magnetic resonance) spectra of compound 6f (DMSO-d6, 300 MHz) at 25–85 °C...
Figure 4: The crystal structure of 6a (CCDC2365306).
Scheme 5: A suggested mechanism for compounds 4.
Scheme 6: Synthesis of pyrrole-fused dibenzoxazepine/triazolobenzodiazepine through a 4-CR.
Scheme 7: Gram-scale synthesis of pyrrole-fused dibenzoxazepine/triazolobenzodiazepine 4a and 6a via 3-CRs.
Figure 5: UV–vis absorption for compounds 4a, 6c and QS (quinine sulfate) (a); emission for 4a, 6c and QS (b)...
C–H Trifluoromethylthiolation of aldehyde hydrazones
- Victor Levet,
- Balu Ramesh,
- Congyang Wang and
- Tatiana Besset
Beilstein J. Org. Chem. 2024, 20, 2883–2890, doi:10.3762/bjoc.20.242
Graphical Abstract
Scheme 1: State of the art and this work.
Scheme 2: Reaction conditions: hydrazone (0.3 mmol, 1.0 equiv), NBS (0.33 mmol, 1.1 equiv), in CH3CN (0.4 M),...
Scheme 3: Scope of the reaction. Reaction conditions: 1 (0.3 mmol, 1.0 equiv), NBS (0.33 mmol, 1.1 equiv) in ...
Scheme 4: Mechanistic investigations and post-functionalization reactions. a19F NMR yields using α,α,α-triflu...
Recent advances in transition-metal-free arylation reactions involving hypervalent iodine salts
- Ritu Mamgain,
- Kokila Sakthivel and
- Fateh V. Singh
Beilstein J. Org. Chem. 2024, 20, 2891–2920, doi:10.3762/bjoc.20.243
Graphical Abstract
Figure 1: Various structures of iodonium salts.
Scheme 1: Αrylation of α-fluoroacetoacetamides 5 to α-aryl-α-fluoroacetoacetamides 7 and α-fluoroacetamides 8...
Scheme 2: Proposed mechanism for the arylation of α-fluoroacetoacetamides 5 to α-aryl-α-fluoroacetoacetamides ...
Scheme 3: α-Arylation of α-nitro- and α-cyano derivatives of α-fluoroacetamides 9 employing unsymmetrical DAI...
Scheme 4: Synthesis of α,α-difluoroketones 13 by reacting α,α-difluoro-β-keto acid esters 11 with aryl(TMP)io...
Scheme 5: Coupling reaction of arynes generated by iodonium salts 6 and arynophiles 14 for the synthesis of t...
Scheme 6: Metal-free arylation of quinoxalines 17 and quinoxalinones 19 with DAISs 16.
Scheme 7: Transition-metal-free, C–C cross-coupling of 2-naphthols 21 to 1-arylnapthalen-2-ols 22 employing d...
Scheme 8: Arylation of vinyl pinacol boronates 23 to trans-arylvinylboronates 24 in presence of hypervalent i...
Scheme 9: Light-induced selective arylation at C2 of quinoline N-oxides 25 and pyridine N-oxides 28 in the pr...
Scheme 10: Plaussible mechanism for the light-induced selective arylation of N-heterobiaryls.
Scheme 11: Photoinduced arylation of heterocycles 31 with the help of diaryliodonium salts 16 activated throug...
Scheme 12: Arylation of MBH acetates 33 with DIPEA and DAIRs 16.
Scheme 13: Aryl sulfonylation of MBH acetates 33 with DABSO and diphenyliodonium triflates 16.
Scheme 14: Synthesis of oxindoles 37 from N-arylacrylamides 36 and diaryliodonium salts 26.
Scheme 15: Mechanically induced N-arylation of amines 38 using diaryliodonium salts 16.
Scheme 16: o-Fluorinated diaryliodonium salts 40-mediated diarylation of amines 38.
Scheme 17: Proposed mechanism for the diarylation of amines 38 using o-fluorinated diaryliodonium salts 40.
Scheme 18: Ring-opening difunctionalization of aliphatic cyclic amines 41.
Scheme 19: N-Arylation of amino acid esters 44 using hypervalent iodonium salts 45.
Scheme 20: Regioselective N-arylation of triazole derivatives 47 by hypervalent iodonium salts 48.
Scheme 21: Regioselective N-arylation of tetrazole derivatives 50 by hypervalent iodonium salt 51.
Scheme 22: Selective arylation at nitrogen and oxygen of pyridin-2-ones 53 by iodonium salts 16 depending on t...
Scheme 23: N-Arylation using oxygen-bridged acyclic diaryliodonium salt 56.
Scheme 24: The successive C(sp2)–C(sp2)/O–C(sp2) bond formation of naphthols 58.
Scheme 25: Synthesis of diarylethers 62 via in situ generation of hypervalent iodine salts.
Scheme 26: O-Arylated galactosides 64 by reacting protected galactosides 63 with hypervalent iodine salts 16 i...
Scheme 27: Esterification of naproxen methyl ester 65 via formation and reaction of naproxen-containing diaryl...
Scheme 28: Etherification and esterification products 72 through gemfibrozil methyl ester-derived diaryliodoni...
Scheme 29: Synthesis of iodine containing meta-substituted biaryl ethers 74 by reacting phenols 61 and cyclic ...
Scheme 30: Plausible mechanism for the synthesis of meta-functionalized biaryl ethers 74.
Scheme 31: Intramolecular aryl migration of trifluoromethane sulfonate-substituted diaryliodonium salts 75.
Scheme 32: Synthesis of diaryl ethers 80 via site-selective aryl migration.
Scheme 33: Synthesis of O-arylated N-alkoxybenzamides 83 using aryl(trimethoxyphenyl)iodonium salts 82.
Scheme 34: Synthesis of aryl sulfides 85 from thiols 84 using diaryliodonium salts 16 in basic conditions.
Scheme 35: Base-promoted synthesis of diarylsulfoxides 87 via arylation of general sulfinates 86.
Scheme 36: Plausible mechanism for the arylation of sulfinates 86 via sulfenates A to give diaryl sulfoxides 87...
Scheme 37: S-Arylation reactions of aryl or heterocyclic thiols 88.
Scheme 38: Site-selective S-arylation reactions of cysteine thiol groups in 91 and 94 in the presence of diary...
Scheme 39: The selective S-arylation of sulfenamides 97 using diphenyliodonium salts 98.
Scheme 40: Plausible mechanism for the synthesis of sulfilimines 99.
Scheme 41: Synthesis of S-arylxanthates 102 by reacting DAIS 101 with potassium alkyl xanthates 100.
Figure 2: Structured of the 8-membered and 4-membered heterotetramer I and II.
Scheme 42: S-Arylation by diaryliodonium cations 103 using KSCN (104) as a sulfur source.
Scheme 43: S-Arylation of phosphorothioate diesters 107 through the utilization of diaryliodonium salts 108.
Scheme 44: Transfer of the aryl group from the hypervalent iodonium salt 108 to phosphorothioate diester 107.
Scheme 45: Synthesis of diarylselenides 118 via diarylation of selenocyanate 115.
Scheme 46: Light-promoted arylation of tertiary phosphines 119 to quaternary phosphonium salts 121 using diary...
Scheme 47: Arylation of aminophosphorus substrate 122 to synthesize phosphine oxides 123 using aryl(mesityl)io...
Scheme 48: Reaction of diphenyliodonium triflate (16) with DMSO (124) via thia-Sommelet–Hauser rearrangement.
Scheme 49: Synthesis of biaryl compounds 132 by reacting diaryliodonium salts 131 with arylhydroxylamines 130 ...
Scheme 50: Synthesis of substituted indazoles 134 and 135 from N-hydroxyindazoles 133.
The charge transport properties of dicyanomethylene-functionalised violanthrone derivatives
- Sondos A. J. Almahmoud,
- Joseph Cameron,
- Dylan Wilkinson,
- Michele Cariello,
- Claire Wilson,
- Alan A. Wiles,
- Peter J. Skabara and
- Graeme Cooke
Beilstein J. Org. Chem. 2024, 20, 2921–2930, doi:10.3762/bjoc.20.244
Graphical Abstract
Figure 1: Chemical structures of violanthrone and dihydroxyviolanthrone.
Figure 2: Chemical structures of 2b and 3b.
Scheme 1: Synthesis of compounds 2a–c and 3a–c.
Figure 3: Optimised ground state geometries of compounds 2 and 3 calculated using B3LYP/6-311G(d,p) in the ga...
Figure 4: Views of the crystal structure of 3b (left, shows displacement ellipsoids drawn at 50% probability ...
Figure 5: Absorption spectra of 3a–c measured in dichloromethane solution (1 × 10−5 M).
Figure 6: SWV (left) and CV (right) of compound 3a–c (in dichloromethane 1 × 10−3 M) (V vs Fc/Fc+).
Structure and thermal stability of phosphorus-iodonium ylids
- Andrew Greener,
- Stephen P. Argent,
- Coby J. Clarke and
- Miriam L. O’Duill
Beilstein J. Org. Chem. 2024, 20, 2931–2939, doi:10.3762/bjoc.20.245
Graphical Abstract
Figure 1: Structure and stability of hypervalent iodine compounds.
Figure 2: Phosphorus-iodonium ylids investigated in this study: Yields (for synthetic procedures, see Supporting Information File 1), stru...
Figure 3: (a) Selected TGA thermograms of phosphorus-iodonium ylids at 10 °C min−1 in N2 (full dataset in Supporting Information File 1). ...
Figure 4: (a) Proposed decomposition mechanism based on ex situ analysis (1H, 31P NMR, ESI-MS) following abor...
4,6-Diaryl-5,5-difluoro-1,3-dioxanes as chiral dopants for liquid crystal compositions
- Maurice Médebielle,
- Peer Kirsch,
- Jérémy Merad,
- Carolina von Essen,
- Clemens Kühn and
- Andreas Ruhl
Beilstein J. Org. Chem. 2024, 20, 2940–2945, doi:10.3762/bjoc.20.246
Graphical Abstract
Figure 1: Selected examples of chiral dopants with high HTPs in their nematic host LC mixture.
Scheme 1: Structure–property relationship of 4,6-diheteroaryl-5,5-difluoro-1,3-dioxanes as potential chiral d...
Scheme 2: The syntheses of chiral 4,6-diphenyl-5,5-difluoro-1,3-dioxanes 3 and 4 as dopants for cholesteric l...
Scheme 3: Synthesis of rac-2 as precursor of rac-3 and rac-4.
Figure 2: Configuration of (R,R)-3 determined by X-ray crystallography.
Figure 3: Configuration of (R,R)-4 determined by X-ray crystallography.
gem-Difluorovinyl and trifluorovinyl Michael acceptors in the synthesis of α,β-unsaturated fluorinated and nonfluorinated amides
- Monika Bilska-Markowska,
- Marcin Kaźmierczak,
- Wojciech Jankowski and
- Marcin Hoffmann
Beilstein J. Org. Chem. 2024, 20, 2946–2953, doi:10.3762/bjoc.20.247
Graphical Abstract
Scheme 1: Generation of gem-difluorovinyl and trifluorovinyl Michael acceptors and their use in the synthesis...
Scheme 2: Formation of α,β-difluorinated and α-fluorinated α,β-unsaturated amides.
Scheme 3: Formation of β-fluorinated and nonfluorinated α,β-unsaturated amides.
Scheme 4: Michael addition of 1a–d with tert-BuLi.
Scheme 5: Michael addition of 2a–d with tert-BuLi.
Scheme 6: Formation of N-methylation products.
Synthesis of fluorinated acid-functionalized, electron-rich nickel porphyrins
- Mike Brockmann,
- Jonas Lobbel,
- Lara Unterriker and
- Rainer Herges
Beilstein J. Org. Chem. 2024, 20, 2954–2958, doi:10.3762/bjoc.20.248
Graphical Abstract
Scheme 1: Synthesis of the starting materials 16, 17, and 18 for the subsequent Williamson ether synthesis wi...
Scheme 2: Synthesis of perfluoroalkyl ester-functionalized aldehydes 22, 23, and 24. Conditions: a) NIS, TFA,...
Scheme 3: Porphyrin synthesis. a) Rothemund porphyrin synthesis of metal-free porphyrins 26, 27, and 28; b) m...
Advances in radical peroxidation with hydroperoxides
- Oleg V. Bityukov,
- Pavel Yu. Serdyuchenko,
- Andrey S. Kirillov,
- Gennady I. Nikishin,
- Vera A. Vil’ and
- Alexander O. Terent’ev
Beilstein J. Org. Chem. 2024, 20, 2959–3006, doi:10.3762/bjoc.20.249
Graphical Abstract
Scheme 1: Organic peroxide initiators in polymer chemistry.
Scheme 2: Synthesis of organic peroxides.
Scheme 3: Richness of radical cascades with species formed from hydroperoxides in redox conditions.
Scheme 4: Co-catalyzed allylic peroxidation of alkenes 1 and 3 by TBHP.
Scheme 5: Allylic peroxidation of alkenes 6 by Pd(II)TBHP.
Scheme 6: Cu(I)-catalyzed allylic peroxidation.
Scheme 7: Enantioselective peroxidation of alkenes 10 with TBHP in the presence of copper(I) compounds.
Scheme 8: Oxidation of α-pinene (12) by the Cu(I)/TBHP system.
Scheme 9: Introduction of the tert-butylperoxy fragment into the α-position of cyclic ketones 15 and 17.
Scheme 10: α-Peroxidation of β-dicarbonyl compounds 19 using the Cu(II)/TBHP system.
Scheme 11: Co-catalyzed peroxidation of cyclic compounds 21 with TBHP.
Scheme 12: Co-, Mn- and Fe-catalyzed peroxidation of 2-oxoindoles 23, barbituric acids 25, and 4-hydroxycoumar...
Scheme 13: Cu-catalyzed and metal-free peroxidation of barbituric acid derivatives 31 and 3,4-dihydro-1,4-benz...
Scheme 14: Electrochemical peroxidation of 1,3-dicarbonyl compounds 35.
Scheme 15: Peroxidation of β-dicarbonyl compounds, cyanoacetic esters and malonic esters 37 by the TBAI/TBHP s...
Scheme 16: Cu-catalyzed peroxidation of malonodinitriles and cyanoacetic esters 39 with TBHP.
Scheme 17: Mn-catalyzed remote peroxidation via trifluromethylation of double bond.
Scheme 18: Cu-catalyzed remote peroxidation via trifluromethylthiolation of double bond.
Scheme 19: Fe-, Mn-, and Ru-catalyzed peroxidation of alkylaromatics 45, 47, 49, and 51 with TBHP.
Scheme 20: Cu-catalyzed peroxidation of diphenylacetonitrile (53) with TBHP.
Scheme 21: Cu-catalyzed peroxidation of benzyl cyanides 60 with TBHP.
Scheme 22: Synthesis of tert-butylperoxy esters 63 from benzyl alcohols 62 using the TBAI/TBHP system.
Scheme 23: Enantioselective peroxidation of 2-phenylbutane (64) with TBHP and chiral Cu(I) complex.
Scheme 24: Photochemical synthesis of peroxides 67 from carboxylic acids 66.
Scheme 25: Photochemical peroxidation of benzylic C(sp3)–H.
Scheme 26: Cu- and Ru-catalyzed peroxidation of alkylamines with TBHP.
Scheme 27: Peroxidation of amides 76 with the TBAI/TBHP system.
Scheme 28: Fe-catalyzed functionalization of ethers 78 with TBHP.
Scheme 29: Synthesis of 4-(tert-butylperoxy)-5-phenyloxazol-2(3H)-ones 82 from benzyl alcohols 80 and isocyana...
Scheme 30: Fe- and Co-catalyzed peroxidation of alkanes with TBHP.
Scheme 31: Rh-catalyzed tert-butylperoxy dienone synthesis with TBHP.
Scheme 32: Rh- and Cu-catalyzed phenolic oxidation with TBHP.
Scheme 33: Metal-free peroxidation of phenols 94.
Scheme 34: Cu-catalyzed alkylation–peroxidation of acrylonitrile.
Scheme 35: Cu-catalyzed cycloalkylation–peroxidation of coumarins 99.
Scheme 36: Metal-free cycloalkylation–peroxidation of coumarins 102.
Scheme 37: Difunctionalization of indene 104 with tert-butylperoxy and alkyl groups.
Scheme 38: Acid-catalyzed radical addition of ketones (108, 111) and TBHP to alkenes 107 and acrylates 110.
Scheme 39: Cu-catalyzed alkylation–peroxidation of alkenes 113 with TBHP and diazo compounds 114.
Scheme 40: Cobalt(II)-catalyzed addition of TBHP and 1,3-dicarbonyl compound 116 to alkenes 117.
Scheme 41: Cu(0)- or Co(II)-catalyzed addition of TBHP and alcohols 120 to alkenes 119.
Scheme 42: Fe-catalyzed functionalization of allenes 122 with TBHP.
Scheme 43: Fe-catalyzed alkylation–peroxidation of alkenes 125 and 127.
Scheme 44: Fe- and Co-catalyzed alkylation–peroxidation of alkenes 130, 133 and 134 with TBHP and aldehydes as...
Scheme 45: Carbonylation–peroxidation of alkenes 137, 140, 143 with hydroperoxides and aldehydes.
Scheme 46: Carbamoylation–peroxidation of alkenes 146 with formamides and TBHP.
Scheme 47: TBAB-catalyzed carbonylation–peroxidation of alkenes.
Scheme 48: VOCl2-catalyzed carbonylation–peroxidation of alkenes 152.
Scheme 49: Acylation–peroxidation of alkenes 155 with aldehydes 156 and TBHP using photocatalysis.
Scheme 50: Cu-catalyzed peroxidation of styrenes 158.
Scheme 51: Fe-catalyzed acylation-peroxidation of alkenes 161 with carbazates 160 and TBHP.
Scheme 52: Difunctionalization of alkenes 163, 166 with TBHP and (per)fluoroalkyl halides.
Scheme 53: Difunctionalization of alkenes 169 and 172 with hydroperoxides and sodium (per)fluoromethyl sulfina...
Scheme 54: Trifluoromethylation–peroxidation of styrenes 175 using MOF Cu3(BTC)2 as a catalyst.
Scheme 55: Difunctionalization of alkenes 178 with tert-butylperoxy and dihalomethyl fragments.
Scheme 56: Difunctionalization of alkenes 180 with the tert-butylperoxy and dihalomethyl moieties.
Scheme 57: The nitration–peroxidation of alkenes 182 with t-BuONO and TBHP.
Scheme 58: Azidation–peroxidation of alkenes 184 with TMSN3 and TBHP.
Scheme 59: Co-catalyzed bisperoxidation of butadiene 186.
Scheme 60: Bisperoxidation of styrene (189) and acrylonitrile (192) with TBHP by Minisci.
Scheme 61: Mn-catalyzed synthesis of bis(tert-butyl)peroxides 195 from styrenes 194.
Scheme 62: Bisperoxidation of arylidene-9H-fluorenes 196 and 3-arylidene-2-oxoindoles 198 with TBHP under Mn-c...
Scheme 63: Synthesis of bisperoxides from styrenes 200 and 203 using the Ru and Rh catalysis.
Scheme 64: Iodine-catalyzed bisperoxidation of styrenes 206.
Scheme 65: Synthesis of di-tert-butylperoxyoxoindoles 210 from acrylic acid anilides 209 using a Pd(II)/TBHP o...
Scheme 66: Pinolation/peroxidation of styrenes 211 catalyzed by Cu(I).
Scheme 67: TBAI-catalyzed acyloxylation–peroxidation of alkenes 214 with carboxylic acids and TBHP.
Scheme 68: Difunctionalization of alkenes 217 with TBHP and water or alcohols.
Scheme 69: TBAI-catalyzed hydroxyperoxidation of 1,3-dienes 220.
Scheme 70: Hydroxyperoxidation of 1,3-dienes 220.
Scheme 71: Iodination/peroxidation of alkenes 223 with I2 and hydroperoxides.
Scheme 72: The reactions of cyclic enol ethers 226 and 228 with I2/ROOH system.
Scheme 73: Synthesis of 1-(tert-butylperoxy)-2-iodoethanes 231.
Scheme 74: Synthesis of 1-iodo-2-(tert-butylperoxy)ethanes 233.
Scheme 75: Cu-catalyzed phosphorylation–peroxidation of alkenes 234.
Scheme 76: Co-catalyzed phosphorylation–peroxidation of alkenes 237.
Scheme 77: Ag-catalyzed sulfonylation–peroxidation of alkenes 241.
Scheme 78: Co-catalyzed sulfonylation–peroxidation of alkenes 244.
Scheme 79: Synthesis of α/β-peroxysulfides 248 and 249 from styrenes 247.
Scheme 80: Cu-catalyzed trifluoromethylthiolation–peroxidation of alkenes 250 and allenes 252.
Scheme 81: Photocatalytic sulfonyl peroxidation of alkenes 254 via deamination of N-sulfonyl ketimines 255.
Scheme 82: Photoredox-catalyzed 1,4-peroxidation–sulfonylation of enynones 257.
Scheme 83: Cu-catalyzed silylperoxidation of α,β-unsaturated compounds 260 and enynes 261.
Scheme 84: Fe-catalyzed silyl peroxidation of alkenes.
Scheme 85: Cu-catalyzed germyl peroxidation of alkenes 267.
Scheme 86: TBAI-catalyzed intramolecular cyclization of diazo compounds 269 with further peroxidation.
Scheme 87: Co-catalyzed three-component coupling of benzamides 271, diazo compounds 272 and TBHP.
Scheme 88: Co-catalyzed esterification-peroxidation of diazo compounds 274 with TBHP and carboxylic acids 275.
Scheme 89: Cu-catalyzed alkylation–peroxidation of α-carbonylimines 277 or ketones 280.
Scheme 90: Mn-catalyzed ring-opening peroxidation of cyclobutanols 282 with TBHP.
Scheme 91: Peroxycyclization of tryptamines 284 with TBHP.
Scheme 92: Radical cyclization–peroxidation of homotryptamines 287.
Scheme 93: Iodine-catalyzed oxidative coupling of indoles 288, cyanoacetic esters and TBHP.
Scheme 94: Summary of metal-catalyzed peroxidation processes.
