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

• analysis of the isolated products of S–H and N–H insertion was carried out based on spectroscopic data (1H and 13C NMR) and the structures of two representatives were established by using the X-ray single crystal diffraction analysis method. Biological activity (cytotoxicity) of some selected products

• derived from 5-mercapto-1H-tetrazoles was also examined. Keywords: 2,5-dihydro-1,3,4-thiadiazoles; enolizable 5-mercapto-1H-tetrazoles; insertion reactions; thiiranes; thiocarbonyl ylides; X-ray analysis; Introduction Cycloaddition reactions, including 1,3-dipolar cycloadditions, are considered as one

• this product, without contamination with 10k, was feasible. Thioaminal 9i and dithioacetal 10i derived from 1-cyclohexyl-5-mercapto-4H-tetrazole (4b) could be isolated as stable, crystalline products and the postulated structures were unambiguously confirmed by the single crystal X-ray diffraction

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

• byproduct and exhibited similar polarity as compound 5. The obtained compounds 3, 4, and 5 were identified using nuclear magnetic resonance (NMR) spectroscopy and mass spectrometry (MS) (see Supporting Information File 1) as well as single crystal X-ray diffraction analysis (vide infra). Furthermore, the

• ruled out. The structures of compounds 3, 4, and 5 were determined by X-ray diffraction analysis (Figure 2). Mono-olefin 3 and bis-olefin 5 adopt a bathtub-like chiral macrocyclic structure rather than figure-eight conformation. Both compounds crystallize as a racemic pair of enantiomers with P21/c and

• has been confirmed by X-ray diffraction analysis. On the other hand, the treatment of bis-olefin 5 under the same conditions recovered the starting material, which highlights the distinctive role of the carbonyl group for the reductive carbon–carbon-bond formation from 3. Conclusion The Wittig

Advances in nitrogen-containing helicenes: synthesis, chiroptical properties, and optoelectronic applications

• Meng Qiu,
• Jing Du,
• Nai-Te Yao,
• Xin-Yue Wang and
• Han-Yuan Gong

Beilstein J. Org. Chem. 2025, 21, 1422–1453, doi:10.3762/bjoc.21.106

• in solution and structurally confirmed via single-crystal X-ray diffraction. It demonstrated the highest CPL performance among the series, with a |glum| value of 3.5 × 10−3 and a photoluminescence quantum yield (PLQY) of 0.31, indicating its potential as a chiral emissive material. Building upon this

Reactions of acryl thioamides with iminoiodinanes as a one-step synthesis of N-sulfonyl-2,3-dihydro-1,2-thiazoles

• Vladimir G. Ilkin,
• Pavel S. Silaichev,
• Valeriy O. Filimonov,
• Tetyana V. Beryozkina,
• Margarita D. Likhacheva,
• Pavel A. Slepukhin,
• Wim Dehaen and
• Vasiliy A. Bakulev

Beilstein J. Org. Chem. 2025, 21, 1397–1403, doi:10.3762/bjoc.21.104

• 2,3-dihydro-1,2-thiazole ring are in the range of 75.3–72.4 ppm and signals of the carbon atom of the cyano group in the range of 117.7–116.6 ppm. The structure of 2,3-dihydro-1,2-thiazole 3aa was additionally confirmed by single crystal X-ray diffraction (Figure 2). According to the X-ray diffraction

• (1.5 mL) was added dropwise. The reaction vessel was removed from the ice bath and the reaction mass was stirred for 10–30 min, then transferred to a silica gel column and the corresponding 2-sulfonyl-1,3-thiazole 3 was isolated. X-ray structure determination of 3aa. Crystal data for C21H21N3O3S2 (M

• final R1 = 0.0584, wR2 = 0.1508 (I > 2σ(I)) and R1 = 0.1081, wR2 = 0.2069 (all data). GooF = 1.027. Largest diff. peak/hole 0.31/−0.40 eÅ−3. The experiment was performed on an automatic four-circle X-ray diffractometer "Xcalibur 3" with a CCD detector according to the standard procedure (Mo Kα

Oxetanes: formation, reactivity and total syntheses of natural products

• Peter Gabko,
• Martin Kalník and
• Maroš Bella

Beilstein J. Org. Chem. 2025, 21, 1324–1373, doi:10.3762/bjoc.21.101

• was generally accepted that this cyclic ether is planar but this myth was eventually debunked by Luger and Buschmann in 1984 who carried out the first X-ray analysis of oxetane [2] and calculated a small puckering angle of 8.7° at 140 K, which is much smaller than the approximate 30° puckering angle

Selective monoformylation of naphthalene-fused propellanes for methylene-alternating copolymers

• Kenichi Kato,
• Tatsuki Hiroi,
• Seina Okada,
• Shunsuke Ohtani and
• Tomoki Ogoshi

Beilstein J. Org. Chem. 2025, 21, 1183–1191, doi:10.3762/bjoc.21.95

• heating process. T90 and CY of [3.3.3]_branch (415 °C and 64 wt %) were lower than those of [3.3.3]_linear because of two-step decay profile (Figure S703a in Supporting Information File 1). All the samples showed broad powder X-ray diffraction (PXRD) patterns with unclear peaks at around 2θ = 11° and 20

A multicomponent reaction-initiated synthesis of imidazopyridine-fused isoquinolinones

• Ashutosh Nath,
• John Mark Awad and
• Wei Zhang

Beilstein J. Org. Chem. 2025, 21, 1161–1169, doi:10.3762/bjoc.21.92

• , Supporting Information File 1), but it was not stable enough for isolation. The structure of 8a was confirmed by single crystal X-ray diffraction analysis. The optimized reaction conditions were used to evaluate the substrate scope of the synthesis of imidazopyridine-fused isoquinolinones 8 (Scheme 3). The

• detected by LC–MS from the reaction mixture. The X-ray structure of 6t indicated that the diene and dienophile are perpendicular to each other which prevents them from being properly aligned for the IMDA reaction. The transition state of the IMDA is electronically destabilized by the sulfur group of the

• chromatography with 30:70 EtOAc/hexanes. Product structures were confirmed by 1H and 13C NMR analysis and X-ray crystal structure analysis of 8a. Density functional theory (DFT) calculations DFT computations were conducted utilizing Gaussian 16W with the B3LYP functional and the 6-31G(d,p) basis set [21][22

Synthetic approach to borrelidin fragments: focus on key intermediates

• Yudhi Dwi Kurniawan,
• Zetryana Puteri Tachrim,
• Teni Ernawati,
• Faris Hermawan,
• Ima Nurasiyah and
• Muhammad Alfin Sulmantara

Beilstein J. Org. Chem. 2025, 21, 1135–1160, doi:10.3762/bjoc.21.91

• a cancer therapeutic, exhibiting anti-inflammatory, anti-angiogenic, antimicrobial, antifungal, and antimalarial activities. While Keller-Schierlein first determined its chemical structure, Anderson later confirmed its absolute configuration using X-ray crystallography [16]. During the screening of

Investigations of amination reactions on an antimalarial 1,2,4-triazolo[4,3-a]pyrazine scaffold

• Henry S. T. Smith,
• Ben Giuliani,
• Kanchana Wijesekera,
• Kah Yean Lum,
• Sandra Duffy,
• Aaron Lock,
• Jonathan M. White,
• Vicky M. Avery and
• Rohan A. Davis

Beilstein J. Org. Chem. 2025, 21, 1126–1134, doi:10.3762/bjoc.21.90

• undescribed amine analogues 2–15 were fully characterised following 1D/2D NMR, UV, and HRMS data analyses. X-ray crystallographic analysis of crystals obtained from the aminated products 2, 7, 10, and 15 are also reported here. The new library of amine-substituted triazolopyrazines was screened against the

• with relevant position numbering. Crystals obtained for 2 were analysed by X-ray crystallographic studies and confirmed the NMR-based structure assignment. The crystal structure of 2 is shown as a thermal ellipsoid plot below (Figure 3). With a simplified approach for the synthesis of aminated

• NMR and HRESIMS data. Further X-ray crystallographic studies were undertaken on crystalline material of compounds 7, 10, and 15. The thermal ellipsoid plots for these compounds are shown in Figure 4. It is notable that piperidine, both at room temperature and under reflux, has been reported to give

Gold extraction at the molecular level using α- and β-cyclodextrins

• Susana Santos Braga

Beilstein J. Org. Chem. 2025, 21, 1116–1125, doi:10.3762/bjoc.21.89

• the constant composition of 2:1 for α-CD to KAuBr4, in consistency with the single-crystal X-ray data. Application studies in gold mining facilities Process patenting and scale-up pilot trials in the United States: The discovery that α-CD can quickly precipitate gold, as detailed in the previous

• desorption of KAu(CN)2. The ability of α-CD to strip gold from carbon was shown to result from the formation of inclusion complexes directly with the cyanoaurate ions, with (at least) two different stoichiometries of α-CD:KAu(CN)2, 1:1 and 2:2. Structural elucidation was achieved by isolation and X-ray

Supramolecular assembly of hypervalent iodine macrocycles and alkali metals

• Krishna Pandey,
• Lucas X. Orton,
• Grayson Venus,
• Waseem A. Hussain,
• Toby Woods,
• Lichang Wang and
• Kyle N. Plunkett

Beilstein J. Org. Chem. 2025, 21, 1095–1103, doi:10.3762/bjoc.21.87

• Krishna Pandey Lucas X. Orton Grayson Venus Waseem A. Hussain Toby Woods Lichang Wang Kyle N. Plunkett School of Chemical and Biomolecular Sciences, Southern Illinois University, Carbondale, IL 62901, United States George L. Clark X-ray Facility and 3M Materials Laboratory, University of Illinois

• NaBArF24. Supporting Information Supporting Information File 29: Detailed experimental procedures, NMR spectra, and X-ray crystallography details. Supporting Information File 30: Crystallographic Information Files for 1/LiBArF20 and 1/NaBArF24. Funding We thank the National Science Foundation (#2003654

Recent total synthesis of natural products leveraging a strategy of enamide cyclization

• Chun-Yu Mi,
• Jia-Yuan Zhai and
• Xiao-Ming Zhang

Beilstein J. Org. Chem. 2025, 21, 999–1009, doi:10.3762/bjoc.21.81

• cyclization to form products in high yields and excellent enantioselectivities. Notably, only a single diastereomer was produced in each case. The single-crystal X-ray crystallography revealed a cis-configuration for both the alkene and ketone substituents on the enamide, indicating that the intramolecular

Studies on the syntheses of β-carboline alkaloids brevicarine and brevicolline

• Benedek Batizi,
• Patrik Pollák,
• András Dancsó,
• Péter Keglevich,
• Gyula Simig,
• Balázs Volk and
• Mátyás Milen

Beilstein J. Org. Chem. 2025, 21, 955–963, doi:10.3762/bjoc.21.79

• catalyst, overreduced product 31, i.e., the tetrahydro derivative of racemic brevicolline ((±)-1) was obtained in 91% yield. Structure determination of 31 was supported by single-crystal X-ray diffraction, as well (Figure 2). Changing the catalyst [Pd(OH)2, Ru, Rh], did not alter the course of the reaction

• -carbolines. Some surprising reactions were also observed, such as the unexpected formation of racemic tetrahydrobrevicolline and the trifluoroethylation of the pyrrole moiety, which can also serve as favorable starting points for further research. The structure of brevicolline ((S)-1) and brevicarine (2). X

• -ray structure of compound 31. Synthesis of racemic brevicolline ((±)-1) starting from 1-methyl-9H-β-carbolin-4-yl trifluoromethanesulfonate (3). Synthesis of brevicarine (2) from brevicolline ((S)-1). First total synthesis of brevicarine (2). Multistep synthesis of brevicarine (2) starting from

Harnessing tethered nitreniums for diastereoselective amino-sulfonoxylation of alkenes

• Shyam Sathyamoorthi,
• Appasaheb K. Nirpal,
• Dnyaneshwar A. Gorve and
• Steven P. Kelley

Beilstein J. Org. Chem. 2025, 21, 947–954, doi:10.3762/bjoc.21.78

• diacetate was necessary for product formation (Table 3, products 20 and 25–28). X-ray crystallographic analysis of 20 (CCDC 2391529) allowed us to unambiguously determine its identity and relative stereochemistry, and we have assigned other products by analogy. A variety of carbamate substrates were

• functional group compatibility. Supporting Information Supporting Information File 2: Additional experimental details including reaction procedures, X-ray crystallographic data, and NMR spectra of synthesized compounds. Acknowledgements Justin Douglas and Sarah Neuenswander (KU NMR Lab) are acknowledged

A convergent synthetic approach to the tetracyclic core framework of khayanolide-type limonoids

• Zhiyang Zhang,
• Jialei Hu,
• Hanfeng Ding,
• Li Zhang and
• Peirong Rao

Beilstein J. Org. Chem. 2025, 21, 926–934, doi:10.3762/bjoc.21.75

• tricyclo[4.2.110,30.11,4]decane ring system. Additionally, krishnolides A and C contain 9–11 stereogenic centers and exhibit diverse oxidation patterns. Their relative and absolute configurations were determined through NMR, HRESIMS and ECD experiments, as well as single crystal X-ray diffraction analysis

• 10 was unequivocally determined through X-ray crystallographic analysis (ORTEP drawing, Scheme 4). Further optimization by elevating the reaction temperature did not noticeably alter the ratio of 32 and 33 (Table 1, entries 8 and 9). Moreover, attempts to apply interrupted Nazarov cyclization with

• ). Construction of α-iodoenone 13. Construction of aldehyde 14. Synthesis of the advanced intermediate 10 (in the X ray structure of 10 solvent molecule is omitted for clarity). Optimization of the interrupted Nazarov cyclization.a Supporting Information Deposition number 2406738 contains the supplementary

Silver(I) triflate-catalyzed post-Ugi synthesis of pyrazolodiazepines

• Muhammad Hasan,
• Anatoly A. Peshkov,
• Syed Anis Ali Shah,
• Andrey Belyaev,
• Chang-Keun Lim,
• Shunyi Wang and
• Vsevolod A. Peshkov

Beilstein J. Org. Chem. 2025, 21, 915–925, doi:10.3762/bjoc.21.74

• trifluoromethyl and nitro groups. Furthermore, substrates 15m–o derived from aliphatic amines, also performed well, furnishing pyrazolodiazepines 16m–o in up to 89% yield. The structure of 16m, a representative compound of this series, was confirmed through single-crystal X-ray diffraction (scXRD) analysis

Dicarboxylate recognition based on ultracycle hosts through cooperative hydrogen bonding and anion–π interactions

• Wen-Hui Mi,
• Teng-Yu Huang,
• Xu-Dong Wang,
• Yu-Fei Ao,
• Qi-Qiang Wang and
• De-Xian Wang

Beilstein J. Org. Chem. 2025, 21, 884–889, doi:10.3762/bjoc.21.72

• . Synthesis of ultracycles. Supporting Information Supporting Information File 4: Experimental details and characterization data (including 1H NMR, 13C NMR, IR, and HRMS of precursor compounds and ultracycles, X-ray data for B4aH, theoretical calculations, and NMR titration data). Funding Financial support

Data accessibility in the chemical sciences: an analysis of recent practice in organic chemistry journals

• Sally Bloodworth,
• Cerys Willoughby and
• Simon J. Coles

Beilstein J. Org. Chem. 2025, 21, 864–876, doi:10.3762/bjoc.21.70

• ., b.p., elemental analysis, optical rotation), thermochemical data, computational data, structure information, cell culture and bioassay data; and excludes X-ray crystallography. ‘NMR’ refers to those examples where a distinct policy for NMR spectroscopic data is available, in addition to the ‘All data

Unraveling cooperative interactions between complexed ions in dual-host strategy for cesium salt separation

• Zhihua Liu,
• Ya-Zhi Chen,
• Ji Wang,
• Qingling Nie,
• Wei Zhao and
• Biao Wu

Beilstein J. Org. Chem. 2025, 21, 845–853, doi:10.3762/bjoc.21.68

• by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures service via https://www.ccdc.cam.ac.uk/. Supporting Information File 50: Nuclear magnetic resonance (NMR), mass and X-ray diffraction data. Acknowledgements We thank support from Analysis

4-(1-Methylamino)ethylidene-1,5-disubstituted pyrrolidine-2,3-diones: synthesis, anti-inflammatory effect and in silico approaches

• Nguyen Tran Nguyen,
• Vo Viet Dai,
• Luc Van Meervelt,
• Do Thi Thao and
• Nguyen Minh Thong

Beilstein J. Org. Chem. 2025, 21, 817–829, doi:10.3762/bjoc.21.65

• spectroscopy, the structure of 4-(1-methylamino)ethylidene-1,5-diphenylpyrrolidine-2,3-dione (5a) was also verified through single-crystal X-ray diffraction. Furthermore, the synthesized molecules were evaluated for compliance with established drug-likeness rules (Lipinski, Veber, Ghose, Egan, and Muegge), as

• single-crystal X-ray diffraction [19]. According to a previous publication, the condensation between pyrrolidine-2,3-diones and an amine as nucleophile normally occurred at the 3-position of nitrogen-containing heterocyclic ring which results in the corresponding enamine product [18]. However, the

• the weaker base, 4-methoxybenzylamine. X-ray study of 4-(1-methylamino)ethylidene-1,5-diphenylpyrrolidine-2,3-dione (5a) Compound 5a crystallizes in the triclinic space group P−1, with one molecule in the asymmetric unit (Figure 2). The pyrrolidine ring is planar (r.m.s. deviation = 0.004 Å) and forms

Acyclic cucurbit[n]uril bearing alkyl sulfate ionic groups

• Christian Akakpo,
• Peter Y. Zavalij and
• Lyle Isaacs

Beilstein J. Org. Chem. 2025, 21, 717–726, doi:10.3762/bjoc.21.55

• alkyl sulfate ionic groups. The X-ray crystal structure of the C1·Me6CHDA complex is reported. Host C1 is significantly less soluble in water (4 mM) compared to the analogous acyclic CB[n] host M1 which features sulfonate ionic groups (346 mM). Host C1 does not undergo significant self-association

• specific guest. C1 binds more tightly to quaternary ammonium guests compared to the corresponding primary ammonium ions. Keywords: cucurbituril; host–guest chemistry; isothermal titration calorimetry; molecular container; X-ray crystallography; Introduction Molecular recognition interactions are key

• spectroscopic characterization of C1 along with determination of its inherent aqueous solubility and self-association properties. Next, we present the X-ray crystal structure of C1 as its C1·Me6CHDA complex. Subsequently, we describe a qualitative investigation of C1·guest and M1·guest complexation by 1H NMR

Origami with small molecules: exploiting the C–F bond as a conformational tool

• Patrick Ryan,
• Ramsha Iftikhar and
• Luke Hunter

Beilstein J. Org. Chem. 2025, 21, 680–716, doi:10.3762/bjoc.21.54

Photochemically assisted synthesis of phenacenes fluorinated at the terminal benzene rings and their electronic spectra

• Yuuki Ishii,
• Minoru Yamaji,
• Fumito Tani,
• Kenta Goto,
• Yoshihiro Kubozono and
• Hideki Okamoto

Beilstein J. Org. Chem. 2025, 21, 670–679, doi:10.3762/bjoc.21.53

• -phenacenes for clarifying the different solid-fluorescence behavior between the parent and fluorinated phenacenes. Although we have extensively examined crystallization of F8-phenacenes, no single crystal suitable for an X-ray diffraction analysis was obtained. The crystalline structural analysis is still

Recent advances in allylation of chiral secondary alkylcopper species

• Minjae Kim,
• Gwanggyun Kim,
• Doyoon Kim,
• Jun Hee Lee and
• Seung Hwan Cho

Beilstein J. Org. Chem. 2025, 21, 639–658, doi:10.3762/bjoc.21.51

• transfer, X-ray crystallographic analysis of the (tert-butyl)(adamantyl)Bpin·Li(THF)2 complex revealed that the B–(adamantyl) bond is shorter than the B–(tert-butyl) bond (1.673 vs 1.692 Å). DFT calculations further illuminated the underlying mechanism by comparing two distinct transition states: TS1

Entry to 2-aminoprolines via electrochemical decarboxylative amidation of N‑acetylamino malonic acid monoesters

• Olesja Koleda,
• Janis Sadauskis,
• Darja Antonenko,
• Edvards Janis Treijs,
• Raivis Davis Steberis and
• Edgars Suna

Beilstein J. Org. Chem. 2025, 21, 630–638, doi:10.3762/bjoc.21.50

• NMR methods, and all attempts to obtain crystals suitable for X-ray crystallographic analysis were unsuccessful. N-Protected 2-aminoproline derivatives 6 are relatively stable under basic conditions as evidenced by successful hydrolysis of the ester moiety in 6a,d,e using aqueous LiOH to provide acids