Search results
Search for "DFT" in Full Text gives 612 result(s) in Beilstein Journal of Organic Chemistry. Showing first 200.
Supramolecular assembly of hypervalent iodine macrocycles and alkali metals
Beilstein J. Org. Chem. 2025, 21, 1095–1103, doi:10.3762/bjoc.21.87
- macrocycle is electrophilic in nature. In addition, DFT results show the three outwardly projected carbonyl oxygens (formerly the carbonyl of benzoic acid) are negatively charged and can potentially bind or interact with metal cations. Figure 3 (right) shows the calculated electrostatic potential map with
- difference in binding constants as well as the isolation of two distinct molecular conformations of phenylalanine HIM 1 (Figure 1), DFT calculations were performed. The details of DFT calculations are shown in Table 1. For DFT calculations, we assigned two HIM macrocycles per LiBArF20 as found in the co
- and I. Without any metal coordination, DFT suggests conformer I is more stable than conformer II by ≈60 kJ/mol. However, upon complexation with Li+, both complexes 2 and 3 are remarkably similar in energy with the difference of less than 1 kJ/mol. This very small energy difference should be too small
Recent advances in synthetic approaches for bioactive cinnamic acid derivatives
Beilstein J. Org. Chem. 2025, 21, 1031–1086, doi:10.3762/bjoc.21.85
Pd-Catalyzed asymmetric allylic amination with isatin using a P,olefin-type chiral ligand with C–N bond axial chirality
Beilstein J. Org. Chem. 2025, 21, 1018–1023, doi:10.3762/bjoc.21.83
- allylic amination of acetate 12 with isatin (11a).a Supporting Information Data of thermal racemization of 7, DFT calculations for investigating racemization mechanism of 7, general methods and materials, experimental procedures and characterization data, 1H, 13C and 31P NMR spectra for 9 and 10, 1H, 13C
Recent total synthesis of natural products leveraging a strategy of enamide cyclization
Beilstein J. Org. Chem. 2025, 21, 999–1009, doi:10.3762/bjoc.21.81
- bridge cycle [36][37]. The excellent diastereoselectivity in this radical cyclization was further rationalized by DFT calculations, which suggests an energy discrepancy of the hydrogen atom transfer process from different faces of the resulting α-hydroxyl radical. Final reduction of the ketone and amide
On the photoluminescence in triarylmethyl-centered mono-, di-, and multiradicals
Beilstein J. Org. Chem. 2025, 21, 964–998, doi:10.3762/bjoc.21.80
- intensity borrowing from higher excited states, due to orbital overlap, does not explain the improved performance sufficiently, especially when comparing the oscillator strengths that can be determined using density functional theory (DFT) studies [19][20][21]. Moreover, when looking at di- or multiradicals
- to break the symmetry. Here, the molecule consists of a pentalchloro phenyl and two tribromophenyl units (PCl-TBr2M) [55], or with two p-bromotetrafluorophenyl rings (PCl-TFBr2M) (see Figure 2d–f) [52]. DFT calculations for these mixed per- and trihalophenylmethyl radicals and their orbitals show a
- . However, one can observe a loss of the vibronic features in the fluorescence signal, indicating that the emission occurs from a CT state, in agreement with the DFT orbital distribution in the ground state geometry (see Figure 2e for different orbital location in HDMO and SOMO). Interestingly, successive
Study of tribenzo[b,d,f]azepine as donor in D–A photocatalysts
Beilstein J. Org. Chem. 2025, 21, 935–944, doi:10.3762/bjoc.21.76
- experimentally in the solvatochromism study of fluorescence using solvents with diverse polarities (see Supporting Information File 1, Figure S9). Indeed, the density functional theory (DFT) calculation performed at WB97XD/Def2TZVP level of theory showed the lowest value for the HOMO–LUMO energy gap in compound
- behavior is supported by the DFT studies, which suggested a better spatial separation between the HOMO and LUMO. As expected, the HOMO–LUMO energy gap followed a trend that is dependent on the electron-donating capacity of the nitrogen heterocycles and amine present in compounds 5e (2.9 eV), 5d (3.5 eV
- CT stabilization of the first excited state of the molecule [34]. This observation is further supported by the orthogonal D–A conformation calculated using DFT, which indicates a decoupled interaction between the HOMO and the LUMO (Figure 2). Moreover, compound 5e is the only member of the family in
Recent advances in controllable/divergent synthesis
Beilstein J. Org. Chem. 2025, 21, 890–914, doi:10.3762/bjoc.21.73
- thiols act as stoichiometric reductants. Mechanistic insights, elucidated through control experiments and DFT calculations, revealed that photoexcitation of diazo imide 41 triggers nitrogen extrusion (ΔG‡ = +10.0 kcal·mol−1), generating the triplet carbene intermediate Int-45. In DCM, this species
- substrates 61. At 10 °C, the catalytic system consisting of NiBr₂(diglyme), oxazoline ligand, (EtO)₃SiH, and K₃PO₄(H₂O) achieved β-selective hydroalkylation. When the temperature was raised to 100 °C, the reaction selectively produced α-branched products. DFT calculations showed that at low temperatures, the
- mechanistic experiments and DFT calculations, the authors proposed a possible mechanism for the reaction: first, DPZ is excited by light to form the excited state DPZ*, which then oxidizes bromide ions through single-electron transfer to generate corresponding radical anions. These radical anions undergo
Dicarboxylate recognition based on ultracycle hosts through cooperative hydrogen bonding and anion–π interactions
Beilstein J. Org. Chem. 2025, 21, 884–889, doi:10.3762/bjoc.21.72
- selectivity for heptanedioate (C72−) was attributed to cooperative hydrogen bonding, anion–π interactions, and a size-matching effect, as supported by DFT optimizations. Keywords: anion–π interactions; anion recognition; hydrogen bonding; dicarboxylates; ultracycles; Introduction Macrocycles containing more
- ), (c) chemical shift changes of Ha versus titration equivalents c(dicarboxylate)/c(B4aH), and (d) association constants of host and guests. (a–c) DFT-optimized structure of the B4aH-C72− complex. The blue dotted lines represent hydrogen bonds and the black dotted lines represent anion–π interactions
Unraveling cooperative interactions between complexed ions in dual-host strategy for cesium salt separation
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
Other Beilstein-Institut Open Science Activities
