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

• solution into chloroform and controllable release into acidic solution [32]. Very recently, it was found that the receptor L alone can further extract solid Li2SO4 into DMSO solution [33], where sulfate binding is sufficiently strong to drive the solid–liquid extraction. DFT calculations suggest that an

Substituent effects in N-acetylated phenylazopyrazole photoswitches

• Radek Tovtik,
• Dennis Marzin,
• Pia Weigel,
• Stefano Crespi and
• Nadja A. Simeth

Beilstein J. Org. Chem. 2025, 21, 830–838, doi:10.3762/bjoc.21.66

• often show higher quantum yields and increased thermal half-life of the metastable state. For the half-life, the choice of the heterocycle is crucial, as revealed through density functional theory (DFT) calculations, which showed that a 5-membered ring promotes the stability of the Z isomer [30]. Within

• predicted using quantum chemistry to describe the Z→E isomerization in azobenzenes, namely: rotation, inversion, inversion-assisted rotation, and concerted inversion depending on the structure of the azobenzene [40][41][42][43][44]. For PAPs, Calbo et al. showed by DFT calculations that the inversion

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

• , while density functional theory (DFT) calculations provided insights into their electronic properties, including reactivity and stability. This comprehensive approach, integrating synthesis, biological evaluation, and computational methods, highlights the potential of 4-(1-methylamino)ethylidene-1,5

• compounds and the reference drug dexamethasone (DEX) against the iNOS enzyme. The interactions between the ligands and the target enzyme were further visualized and analyzed using Discovery Studio software [47]. Density functional theory (DFT) method: The molecular structures of the tested compounds were

Development and mechanistic studies of calcium–BINOL phosphate-catalyzed hydrocyanation of hydrazones

• Carola Tortora,
• Christian A. Fischer,
• Sascha Kohlbauer,
• Alexandru Zamfir,
• Gerd M. Ballmann,
• Jürgen Pahl,
• Sjoerd Harder and
• Svetlana B. Tsogoeva

Beilstein J. Org. Chem. 2025, 21, 755–765, doi:10.3762/bjoc.21.59

• hydrocyanation of hydrazones, catalyzed by a calcium–BINOL phosphate complex, has been studied for the first time both experimentally and computationally with DFT methods. A full catalytic cycle for the enantioselective synthesis of α-hydrazinonitriles is proposed based on insights gained from DFT calculations

• –BINOL phosphate complex as catalyst. Herein, we report the development of the first Ca–BINOL phosphate-catalyzed asymmetric hydrocyanation of hydrazones and the results from DFT calculations to elucidate the mechanism of this transformation. Results and Discussion We first set out to study the

• set out to elucidate it by using DFT computations (Figure 2). As we have chosen as substrate in our experiments a self-prepared mixture of E- and Z-isomers (9:1) of N-acyl hydrazone 1, which allows for additional binding to oxophilic calcium via the carbonyl oxygen, we did not know a priori which of

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

• transmetalation sequence (Scheme 6). For secondary boronic esters, Morken and co-workers conducted a systematic investigation to develop an efficient activation strategy [47]. Computational studies using DFT revealed an important relationship between the length of the boron–carbon bonds and the corresponding

• 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

• traditional crotyl addition to acetaldehyde. This methodology represents the first example of highly enantio- and diastereoselective copper-catalyzed allylic substitution that controls vicinal stereogenic centers. DFT calculations revealed that the high enantioselectivity (98:2 er) originates from a face

Photocatalyzed elaboration of antibody-based bioconjugates

• Marine Le Stum,
• Eugénie Romero and
• Gary A. Molander

Beilstein J. Org. Chem. 2025, 21, 616–629, doi:10.3762/bjoc.21.49

• a photoredox reaction, whereas when embedded within the protein, the Ru-based ArM complex promoted histidine modification through an energy-transfer mechanism (Figure 5). Based on DFT calculations, this is permitted by the modification of the energy diagram of the ruthenium complex in the presence

Deep-blue emitting 9,10-bis(perfluorobenzyl)anthracene

• Long K. San,
• Sebastian Balser,
• Brian J. Reeves,
• Tyler T. Clikeman,
• Yu-Sheng Chen,
• Steven H. Strauss and
• Olga V. Boltalina

Beilstein J. Org. Chem. 2025, 21, 515–525, doi:10.3762/bjoc.21.39

• , bulky fluorinated substituents, such as perfluoroalkyls and perfluoroaryls, have been predicted by DFT [16] and shown experimentally [17], to improve the air- and photostability of acene-containing materials, by increasing their electron affinity and/or by sterically blocking reactive sites

Photomechanochemistry: harnessing mechanical forces to enhance photochemical reactions

• Francesco Mele,
• Ana M. Constantin,
• Andrea Porcheddu,
• Raimondo Maggi,
• Giovanni Maestri,
• Nicola Della Ca’ and
• Luca Capaldo

Beilstein J. Org. Chem. 2025, 21, 458–472, doi:10.3762/bjoc.21.33

• resulted in 40% yield. Alternating grinding and irradiation, the authors managed to obtain quantitative conversion of 2.1 to 2.3. Overall, in this work, mechanochemistry worked akin to agitation provided by stirring or heating in solution. In fact, 1H NMR spectroscopy, XRD and DFT analyses showed that

• using an anti-solvent (H2O). To account for the unique outcome of photomechanochemical conditions, the authors performed a DFT study and introduced the concept of mechanosusceptibility. Briefly, they computationally applied a force along the C–C-bond-forming tensor that would result in the formation of

Beyond symmetric self-assembly and effective molarity: unlocking functional enzyme mimics with robust organic cages

• Keith G. Andrews

Beilstein J. Org. Chem. 2025, 21, 421–443, doi:10.3762/bjoc.21.30

• (Figure 9A) [39][40]. For cage 1, DFT calculations suggests a population consisting of perhaps two major conformers (C5, C9), with 3–4 minor contributors (298 K, THF) [39][40], but we can control the preference of these conformers by introducing functionality which favors particular amide orientations [39

Identification and removal of a cryptic impurity in pomalidomide-PEG based PROTAC

• Bingnan Wang,
• Yong Lu and
• Chuo Chen

Beilstein J. Org. Chem. 2025, 21, 407–411, doi:10.3762/bjoc.21.28

• silica gel column chromatography. The LUMO and electrostatic charges of thalidomide and its derivatives by DFT calculation at the ωB97X-D/6-311+G** level. The synthetic route for iVeliparib-AP6. The conversion of byproduct 6 to 10 to facilitate its removal. Effects of the length and functionalization of

The effect of neighbouring group participation and possible long range remote group participation in O-glycosylation

• Rituparna Das and
• Balaram Mukhopadhyay

Beilstein J. Org. Chem. 2025, 21, 369–406, doi:10.3762/bjoc.21.27

Synthesis, structure, ionochromic and cytotoxic properties of new 2-(indolin-2-yl)-1,3-tropolones

• Yurii A. Sayapin,
• Eugeny A. Gusakov,
• Inna O. Tupaeva,
• Alexander D. Dubonosov,
• Igor V. Dorogan,
• Valery V. Tkachev,
• Anna S. Goncharova,
• Gennady V. Shilov,
• Natalia S. Kuznetsova,
• Svetlana Y. Filippova,
• Tatyana A. Krasnikova,
• Yanis A. Boumber,
• Alexey Y. Maksimov,
• Sergey M. Aldoshin and
• Vladimir I. Minkin

Beilstein J. Org. Chem. 2025, 21, 358–368, doi:10.3762/bjoc.21.26

• -(1,1-Dimethyl-1H-benzo[e]indolin-2-yl)-5,6,7-trichloro-1,3-tropolone exhibited high in vitro cytotoxic activity against A431 skin cancer and H1299 lung cancer cell lines. Keywords: cytotoxic activity; fluorescence; o-chloranil; quantum chemical DFT calculations; 1,3-tropolones; X-ray diffraction

• large Stokes shift values (Table 2, Figure 5). This is consistent with the above conclusion about the existence of tautomeric equilibrium 7,8 (OH)–7,8 (NH) in solutions based on NMR data and DFT quantum chemical calculations (Scheme 2). The emission with a larger Stokes shift appears to correspond to

• and DFT quantum chemical calculations for 7a, 7b, 8a and 8b. Supporting Information File 14: Crystallographic information file for compound 7b. Acknowledgements XRD studies were performed in accordance with the State Task, State registration № 124013100858-3 (V. V. Tkachev, G. V. Shilov, S. M

Antibiofilm and cytotoxic metabolites from the entomopathogenic fungus Samsoniella aurantia

• Rita Toshe,
• Syeda J. Khalid,
• Blondelle Matio Kemkuignou,
• Esteban Charria-Girón,
• Paul Eckhardt,
• Birthe Sandargo,
• Kunlapat Nuchthien,
• J. Jennifer Luangsa-ard,
• Till Opatz,
• Hedda Schrey,
• Sherif S. Ebada and
• Marc Stadler

Beilstein J. Org. Chem. 2025, 21, 327–339, doi:10.3762/bjoc.21.23

• simulated using Spartan’10 [26] on the PM6 level of theory [27]. Density-functional theory (DFT) calculations were computed utilizing the Gaussian program package, revision C.01 [28]. The geometry of the conformers was optimized on the B3LYP/6-311+G(2d,p) [29][30][31][32] level of theory with tight cutoffs

• on forces and step size. The IEFPCM solvent model [33] was used to simulate the solvent effects of methanol and frequency calculations were used to determine the conformers as minima. Conformers 4.5 kcal/mol above the lowest energy conformer and double conformers were discarded. Time-dependent DFT

Oxidation of [3]naphthylenes to cations and dications converts local paratropicity into global diatropicity

• Abel Cárdenas,
• Zexin Jin,
• Yong Ni,
• Jishan Wu,
• Yan Xia,
• Francisco Javier Ramírez and
• Juan Casado

Beilstein J. Org. Chem. 2025, 21, 277–285, doi:10.3762/bjoc.21.20

• the fact that the ground electronic state of m-22+ converges into an open-shell diradical structure (more stable than the closed-shell one by 1 kcal/mol at the DFT/(U)B3LYP/6-311G(d,p) level). Both 1 and 2 are composed of a total of 30 π electrons, which correspond to the Hückel count of 4n + 2, with

• , 2000 scans at a resolution better than 4 cm−1 were accumulated to optimize the signal-to-noise ratio. Theoretical methods Quantum chemistry was addressed with the Gaussian 09 suite of programs [28]. DFT calculations were performed at the (U)B3LYP[29][30] level, using the 6-311G* basis set [31]. This

Synthesis and characterizations of highly luminescent 5-isopropoxybenzo[rst]pentaphene

• Islam S. Marae,
• Jingyun Tan,
• Rengo Yoshioka,
• Zakaria Ziadi,
• Eugene Khaskin,
• Serhii Vasylevskyi,
• Ryota Kabe,
• Xiushang Xu and
• Akimitsu Narita

Beilstein J. Org. Chem. 2025, 21, 270–276, doi:10.3762/bjoc.21.19

• optimized by density functional theory (DFT) calculations (Figure S2 in Supporting Information File 1). The optoelectronic properties of BPP-OiPr 3 and BPP-dione 4 were initially investigated by UV–vis absorption spectroscopy in comparison with BPP 2 (Figure 2a). BPP 2 and BPP-OiPr 3 displayed similar and

• (see Table S6 in Supporting Information File 1). BPP-dione 4 exhibited a broad absorption extending to 540 nm with a peak at 305 nm and featureless maxima at 469 and 497 nm, which were in line with the results of time-dependent DFT (TD-DFT) calculations at the M062X/6-311G(d,p) level of theory

• also showed significant differences (Figure S5 in Supporting Information File 1), indicating an intramolecular charge-transfer character both in its ground and excited states [30][31]. DFT calculations were performed to understand the effects of the substituents on the frontier orbitals. As shown in

Effect of substitution position of aryl groups on the thermal back reactivity of aza-diarylethene photoswitches and prediction by density functional theory

• Misato Suganuma,
• Daichi Kitagawa,
• Shota Hamatani and
• Seiya Kobatake

Beilstein J. Org. Chem. 2025, 21, 242–252, doi:10.3762/bjoc.21.16

• reactivity, closely matching the experimental data. These findings offer valuable insights for the design of advanced photochromic materials with tailored thermal and photophysical characteristics. Keywords: aza-diarylethene; DFT calculation; photochromism; prediction; thermal back reactivity; Introduction

• effective methods for predicting the thermal back reactivity, density functional theory (DFT) calculations can be considered [51][58][59][60][61][62]. For example, in previous studies on the thermal back reactivity of diarylbenzene that is an analogue of diarylethene, we found that the M06-2X level of

• prediction of thermal back reactivity. Moreover, we attempt to find the optimal functional for achieving a high correlation with experimental values by DFT calculation. Results and Discussion Photochromic properties in n-hexane Compounds N1–N3 were synthesized according to the procedures described in the

Dioxazolones as electrophilic amide sources in copper-catalyzed and -mediated transformations

• Seungmin Lee,
• Minsuk Kim,
• Hyewon Han and
• Jongwoo Son

Beilstein J. Org. Chem. 2025, 21, 200–216, doi:10.3762/bjoc.21.12

• theory (DFT) calculations, a proposed reaction mechanism is suggested as shown in Figure 3. Initially, copper acetylide INT-11 is formed by the reaction of acetylene with a copper precatalyst, leading to the formation of an N-acyl nitrene acetylide intermediate INT-12 after the incorporation of

• dioxazolone 7. Subsequently, nitrene insertion of INT-12 into the Cu–C bond, forms INT-13, which then undergoes isomerization and protodemetalation, followed by catalyst regeneration, as suggested by the DFT calculations. Finally, the nucleophilic addition of the amine to the electrophilic intermediate INT-15

• , providing the corresponding products (16g–k). Mechanistically, the reaction begins with the generation of the active copper species 17, successively forming INT-19 and INT-20 (Figure 5). The penta-coordinated copper nitrenoid species INT-20, as suggested by DFT calculations, undergoes reductive elimination

Quantifying the ability of the CF₂H group as a hydrogen bond donor

• Matthew E. Paolella,
• Daniel S. Honeycutt,
• Bradley M. Lipka,
• Jacob M. Goldberg and
• Fang Wang

Beilstein J. Org. Chem. 2025, 21, 189–199, doi:10.3762/bjoc.21.11

• ; titration studies; DFT calculations. Acknowledgements High-Performance Computing at the University of Rhode Island and the Massachusetts Green High-Performance Computing Center (MGHPCC) are gratefully acknowledged. Funding This research was made possible by the use of equipment available through the Rhode

Recent advances in organocatalytic atroposelective reactions

• Henrich Szabados and
• Radovan Šebesta

Beilstein J. Org. Chem. 2025, 21, 55–121, doi:10.3762/bjoc.21.6

• ) annulation of enals with ynamides 8 to afford axially chiral 7-arylindolines 9 was reported [20]. The reaction mechanism, rationalized by DFT calculations, is believed to occur through catalyst C3 activation of the substrate 8, dehydration, and deprotonation with tautomerization leading to the enamine

• transformation relies on the catalysis with azolium precatalyst C12 (Scheme 11a). The reaction also allowed the synthesis of indol-derived bridged biaryls 35 (Scheme 11b). The proposed mechanism, supported by DFT calculations, comprises propargylic substitution towards Int-20 with NHC-derived enolate Int-19

• 196a–k (Scheme 58) [88]. Both organocatalysts showed comparable effectivity in terms of enantioselectivity across. The difference between these catalysts becomes more visible through DFT calculations. In the case of biaryl phosphoric acid C30, stereocontrol is driven by the steric effects of the groups

Emerging trends in the optimization of organic synthesis through high-throughput tools and machine learning

• Pablo Quijano Velasco,
• Kedar Hippalgaonkar and
• Balamurugan Ramalingam

Beilstein J. Org. Chem. 2025, 21, 10–38, doi:10.3762/bjoc.21.3

Synthesis, structure and π-expansion of tris(4,5-dehydro-2,3:6,7-dibenzotropone)

• Yongming Xiong,
• Xue Lin Ma,
• Shilong Su and
• Qian Miao

Beilstein J. Org. Chem. 2025, 21, 1–7, doi:10.3762/bjoc.21.1

• for conformational change is provided by the earlier report that the NMR spectrum of 1 at −80 °C did not display significant broadening [1]. To better understand the two conformers of 1 found in the crystals, density functional theory (DFT) calculations were carried out using the molecular geometries

• present in the crystal structures. The results showed that C2-1 is more stable than Cs-1 by 3.85 kcal/mol at the B3LYP/6-311G(d,p) level of DFT. Additionally, C2-1 has a smaller gap (3.57 eV) between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) compared

• to Cs-1 (4.37 eV) as calculated at the B3LYP/6-311++G(d,p) level of DFT. The reduced HOMO–LUMO gap of C2-1 can be attributed to the greater conjugation in the essentially flat dibenzotropone moiety. This finding aligns with the fact that the yellow crystal of C2-1 absorbs light of a longer wavelength

Efficient synthesis of fluorinated triphenylenes with enhanced arene–perfluoroarene interactions in columnar mesophases

• Yang Chen,
• Jiao He,
• Hang Lin,
• Hai-Feng Wang,
• Ping Hu,
• Bi-Qin Wang,
• Ke-Qing Zhao and
• Bertrand Donnio

Beilstein J. Org. Chem. 2024, 20, 3263–3273, doi:10.3762/bjoc.20.270

• in Supporting Information File 1). It also shows that the pending fluorophenyl makes an angle of ca. 45° with the triphenylene plane (see also DFT below). Despite this conformational distortion, the molecular thickness, hmol, obtained by dividing the molecular volume with the columnar cross section

• intense, corresponding to a decrease of fluoroarene–arene interactions. This agrees with an increase of the molecular thickness (see hmol values, Table 1), likely due to some electrostatic and steric repulsion between fluorine atoms within the inner core. DFT shows that both triphenylene segments do not

• PH8), with no or little influence of the solvent polarity (Figure 6a). This may suggest that the sigma-bonded F6 and G66 have no conjugation in their ground states, the electron density being located on one triphenylene moiety (see DFT). G66 shows a stronger absorption band than F6, with expected ε

Non-covalent organocatalyzed enantioselective cyclization reactions of α,β-unsaturated imines

• Sergio Torres-Oya and
• Mercedes Zurro

Beilstein J. Org. Chem. 2024, 20, 3221–3255, doi:10.3762/bjoc.20.268

• -position of the activating group with good yields (52–98%), excellent diastereoselectivities and good enantioselectivities (76–94% ee). Additionally, to understand the mechanism of the reaction, the authors performed DFT calculations. Based on the calculations, once the dienolate is hydrolyzed to the free

• mechanism and the origin of the enantioselectivity, the authors performed DFT calculations, highlighting the importance of the outer phenyl ring of the chiral phosphoric acid on the enantioinduction. To demonstrate the synthetic applicability of the chiral axial derivatives a variety of transformations were

Synthesis of 2H-azirine-2,2-dicarboxylic acids and their derivatives

• Anastasiya V. Agafonova,
• Mikhail S. Novikov and
• Alexander F. Khlebnikov

Beilstein J. Org. Chem. 2024, 20, 3191–3197, doi:10.3762/bjoc.20.264

• not isomerize at room temperature, which is typical for highly sterically congested isoxazoles containing a 3-tert-butyl substituent [26]. The mechanism of such isomerizations of isoxazoles has been previously discussed using DFT calculations [25][26], which revealed the formation of an isoxazole–Fe

Direct trifluoroethylation of carbonyl sulfoxonium ylides using hypervalent iodine compounds

• Radell Echemendía,
• Carlee A. Montgomery,
• Fabio Cuzzucoli,
• Antonio C. B. Burtoloso and
• Graham K. Murphy

Beilstein J. Org. Chem. 2024, 20, 3182–3190, doi:10.3762/bjoc.20.263

• reactants. Finally, DFT calculations provided insights about the mechanism of this transformation, which strongly suggest that an SN2 reaction is operative. Keywords: alkylation; DFT calculations; fluorine chemistry; hypervalent iodine; sulfoxonium ylide; sulphur ylides; Introduction Introducing fluorine