Asymmetric total synthesis of tricyclic prostaglandin D2 metabolite methyl ester via oxidative radical cyclization

• Miao Xiao,
• Liuyang Pu,
• Qiaoli Shang,
• Lei Zhu and
• Jun Huang

Beilstein J. Org. Chem. 2025, 21, 1964–1972, doi:10.3762/bjoc.21.152

• ester 4. Optimization of conditions to convert diketone 15 into cyclopentanone 14.a Supporting Information Supporting Information File 42: Experimental procedures, characterization data and copies of 1H and 13C NMR spectra. Acknowledgements We thank Prof. Zhen Yang (Peking University) for helpful

Rhodium-catalysed connective synthesis of diverse reactive probes bearing S(VI) electrophilic warheads

• Scott Rice,
• Julian Chesti,
• William R. T. Mosedale,
• Megan H. Wright,
• Stephen P. Marsden,
• Terry K. Smith and
• Adam Nelson

Beilstein J. Org. Chem. 2025, 21, 1924–1931, doi:10.3762/bjoc.21.150

• ). Outcomes of reactions between α-diazoamide substrates and co-substrates. Supporting Information Supporting Information File 40: Experimental part and NMR spectra of synthesised compounds. Acknowledgements We thank Dan Cox, Samuel Liver, Chris Arter, Jeanine Williams, Mark Howard, Alex Heyam, Lawrence

Synthesis, biological and electrochemical evaluation of glycidyl esters of phosphorus acids as potential anticancer drugs

• Almaz A. Zagidullin,
• Emil R. Bulatov,
• Mikhail N. Khrizanforov,
• Damir R. Davletshin,
• Elvina M. Gilyazova,
• Ivan A. Strelkov and
• Vasily A. Miluykov

Beilstein J. Org. Chem. 2025, 21, 1909–1916, doi:10.3762/bjoc.21.148

• ) shows a singlet at +32 ppm; for diglycidyl methylphosphate (2) and triglycidyl phosphate (3) also a singlet in the region 0–1 ppm is observed, despite the presence of a chiral carbon atom in the oxirane fragment. In the 1H NMR spectra of esters 1–3 the characteristic signals of the oxirane fragment at

• . Experimental General. All reactions and manipulations were carried out under dry pure N2 in standard Schlenk apparatus. All solvents were distilled from sodium/benzophenone or phosphorus pentoxide and stored under nitrogen before use. The NMR spectra were recorded on a Bruker MSL-400 (1H 400 MHz, 31P 161.7 MHz

• , 13C 100.6 MHz). 1H and 13C NMR data are reported with reference to solvent resonances, and 31P NMR spectra were reported with respect to external 85% H3PO4 (0 ppm). All experiments were carried out using standard Bruker pulse programs. Infrared (IR) spectra were recorded on a Bruker Vector-22

Stereoselective electrochemical intramolecular imino-pinacol reaction: a straightforward entry to enantiopure piperazines

• Margherita Gazzotti,
• Fabrizio Medici,
• Valerio Chiroli,
• Laura Raimondi,
• Sergio Rossi and
• Maurizio Benaglia

Beilstein J. Org. Chem. 2025, 21, 1897–1908, doi:10.3762/bjoc.21.147

• procedures and physical data for the new compounds, copies of 1H and 13C NMR spectra of the prepared compounds. Acknowledgements The authors thank Prof. A. Puglisi (Università degli Studi di Milano) for valuable discussions. For the single-crystal X-ray diffraction analysis the Unitech COSPECT (Università

Preparation of spirocyclic oxindoles by cyclisation of an oxime to a nitrone and dipolar cycloaddition

• Beth L. Ritchie,
• Alexandra Longcake and
• Iain Coldham

Beilstein J. Org. Chem. 2025, 21, 1890–1896, doi:10.3762/bjoc.21.146

• are reported. 1H NMR spectra were recorded on a Bruker AC400 (400 MHz) instrument. Chemical shifts are reported in ppm with respect to the residual solvent peaks, with multiplicities given as s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, br = broad. Coupling constants (J values

• ) are quoted to the nearest 0.5 Hz with values in hertz (Hz). 13C NMR spectra were recorded on the above instrument at 100 MHz. Low- and high-resolution (accurate mass) mass spectra were recorded on a Walters LCT instrument using electrospray ionisation (ESI). Synthesis of the aldehyde 4 Sc(OTf)3 (0.63

• : ENaCt protocols, X-ray diffraction data for 5a, and NMR spectra for novel compounds. Acknowledgements We would like to thank Craig Robertson (University of Sheffield) and the EPSRC UK National Crystallography Service for access to ENaCt technology and the collection of associated crystallographic data

Systematic pore lipophilization to enhance the efficiency of an amine-based MOF catalyst in the solvent-free Knoevenagel reaction

• Pricilla Matseketsa,
• Margret Kumbirayi Ruwimbo Pagare and
• Tendai Gadzikwa

Beilstein J. Org. Chem. 2025, 21, 1854–1863, doi:10.3762/bjoc.21.144

• the conversions we obtained using the dodecane calibration curve with those determined by directly comparing the integrations of the benzaldehyde and BMN protons in the 1H NMR spectra, we found little difference (Table S2, Supporting Information File 1). Thus, we decided to discontinue the addition of

• -synthesis modification (PSM). A) Schematic representation of the reaction of KSU-1 with aliphatic isocyanates and the estimated conversions at –OH and –NH2. B) The corresponding 1H NMR spectra of the MOF reaction products digested in a solution of D2SO4 in DMSO-d6. A) Schematic representation of the

• reaction between benzaldehyde and malononitrile to form benzylidenemalononitrile (BMN). B) Representative 1H NMR spectra for the reaction of benzaldehyde and malononitrile in toluene with dodecane as internal standard, analyzed after 30 minutes. Graphical representation of the Knoevenagel catalysis results

[3 + 2] Cycloaddition of thioformylium methylide with various arylidene-azolones in the synthesis of 7-thia-3-azaspiro[4.4]nonan-4-ones

• Daniil I. Rudik,
• Irina V. Tiushina,
• Anatoly I. Sokolov,
• Alexander Yu. Smirnov,
• Alexander R. Romanenko,
• Alexander A. Korlyukov,
• Andrey A. Mikhaylov and
• Mikhail S. Baranov

Beilstein J. Org. Chem. 2025, 21, 1791–1798, doi:10.3762/bjoc.21.141

• . Optimization of the reaction conditionsa. Supporting Information Supporting Information File 22: Experimental part, X-ray data and copies of NMR spectra. Acknowledgements A.A. Korlyukov and A.R. Romanenko are grateful to Ministry of Science and Higher Education of the Russian Federation (Contract No. 075

Synthesis of chiral cyclohexane-linked bisimidazolines

• Changmeng Xi,
• Qingshan Sun and
• Jiaxi Xu

Beilstein J. Org. Chem. 2025, 21, 1786–1790, doi:10.3762/bjoc.21.140

• of chiral cyclohexane-linked bisimidazoline ligands. Supporting Information Supporting Information File 20: Analytical data and copies of 1H and 13C NMR spectra of compounds 2 and 4, copies of HRMS spectra of unknown compounds 4 and 5. Funding This research was supported by the National Key R & D

Preparation of a furfural-derived enantioenriched vinyloxazoline building block and exploring its reactivity

• Madara Darzina,
• Anna Lielpetere and
• Aigars Jirgensons

Beilstein J. Org. Chem. 2025, 21, 1737–1741, doi:10.3762/bjoc.21.136

• proposed mechanism of product 7 formation. Electrochemical oxidation of protected amino alcohol 2d to ester 3d. Supporting Information Supporting Information File 8: Experimental procedures, characterization data and copies of NMR spectra. Funding This project has received funding from the European

Convenient alternative synthesis of the Malassezia-derived virulence factor malassezione and related compounds

• Karu Ramesh and
• Stephen L. Bearne

Beilstein J. Org. Chem. 2025, 21, 1730–1736, doi:10.3762/bjoc.21.135

• . Concentration under reduced pressure refers to the removal of solvent using a rotary evaporator, unless stated otherwise. All NMR spectra were obtained using a Bruker ASCEND 400 MHz spectrometer at the Nuclear Magnetic Resonance Research Resource (NMR-3, Dalhousie University). Chemical shifts (δ in ppm) for

3,3'-Linked BINOL macrocycles: optimized synthesis of crown ethers featuring one or two BINOL units

• Somayyeh Kheirjou,
• Jan Riebe,
• Maike Thiele,
• Christoph Wölper and
• Jochen Niemeyer

Beilstein J. Org. Chem. 2025, 21, 1719–1729, doi:10.3762/bjoc.21.134

• that we reacted either (S)- or (R)-H-2 with the dichloride (S)-iPr-62 to give the diastereomeric macrocycles (S,S)-HiPr-M22 and (R,S)-HiPr-M22 in 73/49% yield, respectively. The 1H NMR spectra of the C2-symmetric derivatives (S,S)-H/iPr-M22 (see Figure 8a/b) differ most significantly in the splitting

• -62; ii) Me/(S)-H/(R)-H/iPr-2 (1.0 equiv), Cs2CO3 (3.2 equiv), CH3CN, 80 °C. 1H NMR spectra of a) (S,S)-H-M22, b) (S,S)-iPr-M22, c) (S,S)-HiPr-M22, and d) (R,S)-HiPr-M22 (all: 400 MHz, CDCl3, 298 K, for labelling see Figure 7). Supporting Information Synthetic procedures and NMR spectra for all new

Structural analysis of stereoselective galactose pyruvylation toward the synthesis of bacterial capsular polysaccharides

• Tsun-Yi Chiang,
• Mei-Huei Lin,
• Chun-Wei Chang,
• Jinq-Chyi Lee and
• Cheng-Chung Wang

Beilstein J. Org. Chem. 2025, 21, 1671–1677, doi:10.3762/bjoc.21.131

• reaction conditions towards the synthesis of (R)-pyruvylated galactose 5 and 6. Supporting Information Supporting Information File 62: Experimental procedures and NMR spectra. Acknowledgements We thank Miss Ping-Yu Lin for Mass, Dr. Ying-Yann Wu for NMR and Dr. Yuh-Sheng Wen for X-ray in Academia Sinica

Formal synthesis of a selective estrogen receptor modulator with tetrahydrofluorenone structure using [3 + 2 + 1] cycloaddition of yne-vinylcyclopropanes and CO

• Jing Zhang,
• Guanyu Zhang,
• Hongxi Bai and
• Zhi-Xiang Yu

Beilstein J. Org. Chem. 2025, 21, 1639–1644, doi:10.3762/bjoc.21.127

• synthesis of 1. Formal synthesis of SERMs molecule VI. Supporting Information Supporting Information File 54: Experimental procedures, product characterizations, and copies of the 1H and 13C NMR spectra. Acknowledgements We thank Zhiqiang Huang for testing the stoichiometric Heck reaction in this

Synthesis of optically active folded cyclic dimers and trimers

• Ena Kumamoto,
• Kana Ogawa,
• Kazunori Okamoto and
• Yasuhiro Morisaki

Beilstein J. Org. Chem. 2025, 21, 1603–1612, doi:10.3762/bjoc.21.124

• and twisted, which caused the different chiroptical properties. Experimental General 1H and 13C NMR spectra were recorded on a JEOL JNM ECZ-500R instrument at 500 and 125 MHz, respectively. Samples were analyzed in CDCl3, and the chemical shift values were expressed relative to Me4Si as an internal

3-Aryl-2H-azirines as annulation reagents in the Ni(II)-catalyzed synthesis of 1H-benzo[4,5]thieno[3,2-b]pyrroles

• Julia I. Pavlenko,
• Pavel A. Sakharov,
• Anastasiya V. Agafonova,
• Derenik A. Isadzhanyan,
• Alexander F. Khlebnikov and
• Mikhail S. Novikov

Beilstein J. Org. Chem. 2025, 21, 1595–1602, doi:10.3762/bjoc.21.123

• charge by the joint Cambridge Crystallographic Data Centre. Supporting Information File 24: Full experimental details, characterization data and copies of NMR spectra for all new compounds. Acknowledgements This research was carried out using resources of the Centre for Magnetic Resonance, the Research

Chemical synthesis of glycan motifs from the antitumor agent PI-88 through an orthogonal one-pot glycosylation strategy

• Shaokang Yang,
• Xingchun Sun,
• Hanyingzi Fan and
• Guozhi Xiao

Beilstein J. Org. Chem. 2025, 21, 1587–1594, doi:10.3762/bjoc.21.122

• was obtained in 60% overall yield from 20 via sequential global deprotection of the Bn, Cbz, and Bz groups. The structures of the synthetic glycan motifs 1–4 were supported by their 1H and 13C NMR spectra and MALDI–TOF as well as ESI mass spectra. In particular, the anomeric proton signals of 1–4 were

• highlighted in the 1H NMR spectra of synthetic glycans motifs 1–4 (see Supporting Information File 1). Conclusion In summary, the monophosphorylated glycan motifs 1–4 from PI-88 have been collectively synthesized via a one-pot orthogonal glycosylation strategy on the basis of glycosyl PVB, which avoids such

pH-Controlled isomerization kinetics of ortho-disubstituted benzamidines: E/Z isomerism and axial chirality

• Ryota Kimura,
• Satoshi Ichikawa and
• Akira Katsuyama

Beilstein J. Org. Chem. 2025, 21, 1568–1576, doi:10.3762/bjoc.21.120

• bond rotation was investigated by variable temperature nuclear magnetic resonance (VT-NMR) spectra (Figure 3) in DMSO-d6 [27]. In the case of the molecular form of amidine 1 (Figure 3a), the signals corresponding to the two methyl groups resulting from the amidine E/Z isomerism were observed separately

• protonated form calculated by the DFT method. Comparison of VT-NMR spectra of a) amidine 1 and b) its trifluoroacetate salt 1-H+ in DMSO-d6 (400 MHz). Separation and isolation of amidine E/Z isomers by RP-HPLC. The mobile phase contained CF3CO2H to protonate the amidine moiety. Kinetic analysis of the

Synthesis of an aza[5]helicene-incorporated macrocyclic heteroarene via oxidation of an o-phenylene-pyrrole-thiophene icosamer

• Yusuke Matsuo,
• Aoi Nakagawa,
• Shu Seki and
• Takayuki Tanaka

Beilstein J. Org. Chem. 2025, 21, 1561–1567, doi:10.3762/bjoc.21.119

• for NHs are omitted for clarity. 1H NMR spectra of 5 in DMSO-d6 (a) at room temperature and (b) at 100 °C. (a) X-ray crystal structure of 5; (left) top view, (right) side view. Thermal ellipsoids are scaled to 50% probability level. Solvent molecules and hydrogen atoms except for NHs are omitted for

• heteroarene 5. Supporting Information Supporting Information File 14: Experimental procedures, characterization data of all products, copies of 1H and 13C NMR spectra, optical data, and DFT calculation results. Supporting Information File 15: Crystallographic Information File for compound 4. Supporting

Facile synthesis of hydantoin/1,2,4-oxadiazoline spiro-compounds via 1,3-dipolar cycloaddition of nitrile oxides to 5-iminohydantoins

• Juliana V. Petrova,
• Varvara T. Tkachenko,
• Victor A. Tafeenko,
• Anna S. Pestretsova,
• Vadim S. Pokrovsky,
• Maxim E. Kukushkin and
• Elena K. Beloglazkina

Beilstein J. Org. Chem. 2025, 21, 1552–1560, doi:10.3762/bjoc.21.118

• -substituted aromatic group, we have observed atropoisomerism (Figure 2) what is manifested by the appearance of a second set of signals in their NMR spectra. As the previously studied similar structures (Y = N–R) [22], products 5b and 5d (Y = O) were formed through the addition of a dipole molecule, resulting

Azide–alkyne cycloaddition (click) reaction in biomass-derived solvent Cyrene^TM under one-pot conditions

• Zoltán Medgyesi and
• László T. Mika

Beilstein J. Org. Chem. 2025, 21, 1544–1551, doi:10.3762/bjoc.21.117

• Supporting Information File 1. 1H, 13C, and 19F NMR spectra were collected on a Bruker Avance 300 MHz or Bruker Avance-III 500 MHz instrument and processed by MestReNova v. 14.3.1-31739 (2022) MestreLab Research S. L. GC analyses were performed on an HP 5890 N Series II instrument with Restek RTX®-50

General method for the synthesis of enaminones via photocatalysis

• Paula Pérez-Ramos,
• Raquel G. Soengas and
• Humberto Rodríguez-Solla

Beilstein J. Org. Chem. 2025, 21, 1535–1543, doi:10.3762/bjoc.21.116

• : Additional optimization details, mechanistic studies, experimental details, characterization data and NMR spectra for enaminones 9. Acknowledgements We would like to thank Prof. Jose Manuel Costa-Fernández for his help with the spectroscopic studies. Funding This work has received financial support from MCI

Calcium waste as a catalyst in the transesterification for demanding esters: scalability perspective

• Anton N. Potorochenko and
• Konstantin S. Rodygin

Beilstein J. Org. Chem. 2025, 21, 1520–1527, doi:10.3762/bjoc.21.114

• initial ethyl esters were observed in the NMR spectra of the reaction mixtures. Remarkably, ethyl 2-bromopropanoate (4d) reacted less successfully in the transesterification and the yield of methyl ester 5d within 2 h was 66%, even when the catalyst loading was increased to 5 wt %. The transesterification

• of NMR spectra. Acknowledgements The authors gratefully acknowledge the Magnetic Resonance Research Centre, Centre for Chemical Analysis and Materials Research, X-ray Diffraction Research Centre of Research Park of Saint Petersburg State University. Funding This work was financially supported by

Ambident reactivity of enolizable 5-mercapto-1H-tetrazoles in trapping reactions with in situ-generated thiocarbonyl S-methanides derived from sterically crowded cycloaliphatic thioketones

• Grzegorz Mlostoń,
• Małgorzata Celeda,
• Marcin Palusiak,
• Heinz Heimgartner,
• Marta Denel-Bobrowska and
• Agnieszka B. Olejniczak

Beilstein J. Org. Chem. 2025, 21, 1508–1519, doi:10.3762/bjoc.21.113

• contained thioaminals 9, which underwent a slow isomerization in CDCl3 solution. Notably, in the case of products 9k and 10k, bearing a Ph group at N(1), after a successful chromatographic separation, the less stable 9k underwent isomerization in CDCl3 solution (at rt) and no registration of NMR spectra of

• observed in the 1H NMR spectra registered for crude reaction mixtures (Table 1). The mechanism of the studied reactions deserves a brief comment and should help to clarify whether the formation of 9 and 10 results from the ambident reactivity of 5-mercapto-1H-tetrazoles, suggested in some earlier

• II and they are uncorrected. NMR spectra were taken with a Bruker AVIII spectrometer (1H NMR (600 MHz); 13C NMR (151 MHz); chemical shifts are relative to residual undeuterated solvent peaks (CDCl3: 1H NMR δ = 7.25, 13C NMR δ = 77.00). Elemental analyses were obtained with a Vario EL III (Elementar

Microwave-enhanced additive-free C–H amination of benzoxazoles catalysed by supported copper

• Andrei Paraschiv,
• Valentina Maruzzo,
• Filippo Pettazzi,
• Stefano Magliocco,
• Paolo Inaudi,
• Daria Brambilla,
• Gloria Berlier,
• Giancarlo Cravotto and
• Katia Martina

Beilstein J. Org. Chem. 2025, 21, 1462–1476, doi:10.3762/bjoc.21.108

• benzoxazole with piperidine. Efficacy of silica-supported Cu(I) and Cu(II) in promoting the C2-amination of benzoxazole with piperidine. Copper-supported catalysts. Supporting Information Supporting Information File 24: Experimental procedures, compound characterization data, and copies of NMR spectra

Wittig reaction of cyclobisbiphenylenecarbonyl

• Taito Moribe,
• Junichiro Hirano,
• Hideaki Takano,
• Hiroshi Shinokubo and
• Norihito Fukui

Beilstein J. Org. Chem. 2025, 21, 1454–1461, doi:10.3762/bjoc.21.107

• slightly preferred at room temperature with approximately a 3:2 ratio of figure-eight and bathtub conformations. We have also estimated the activation barriers of the interconversion of 3 and 5 between the figure-eight and bathtub conformations by measuring VT 1H NMR spectra in toluene-d8 because the

• beneficial for the development of advanced materials. Synthesis and structures of CBBC 1. X-ray crystal structures of (a) 3, (b) 4, and (c) 5 with thermal ellipsoids at 50% probability; all hydrogen atoms are omitted for clarity. VT 1H NMR spectra of 5 in CD2Cl2 at (a) 298 K, (b) 243 K, and (c) 203 K. Blue