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Search for "DFT" in Full Text gives 612 result(s) in Beilstein Journal of Organic Chemistry. Showing first 200.

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

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  • ; 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
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Published 20 Jan 2025

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

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  • ) 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
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Published 09 Jan 2025

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

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Published 06 Jan 2025

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

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  • 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
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Published 02 Jan 2025

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

Graphical Abstract
  • 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
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Published 16 Dec 2024

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

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  • -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
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Published 10 Dec 2024

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

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  • 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
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Published 05 Dec 2024

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

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  • 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
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Published 04 Dec 2024

Controlled oligomerization of [1.1.1]propellane through radical polarity matching: selective synthesis of SF5- and CF3SF4-containing [2]staffanes

  • Jón Atiba Buldt,
  • Wang-Yeuk Kong,
  • Yannick Kraemer,
  • Masiel M. Belsuzarri,
  • Ansh Hiten Patel,
  • James C. Fettinger,
  • Dean J. Tantillo and
  • Cody Ross Pitts

Beilstein J. Org. Chem. 2024, 20, 3134–3143, doi:10.3762/bjoc.20.259

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  • chloropentafluorosulfanylated [2]staffane (SF5-BCP-BCP-Cl, 2), based on alternating radical polarity matching in the chain-propagation steps (Figure 1, bottom) [45][46][47]. Density functional theory (DFT) calculations provide insight into our observed selectivity, and our hypothesis is bolstered by computation of relative
  • established that [1.1.1]propellane participates in radical-chain reactions (i.e., oligomerization) at room temperature in solution to form unsubstituted [n]staffanes. The origin of this innately controlled oligomerization was then investigated through density functional theory (DFT) calculations. The free
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Published 29 Nov 2024

Hypervalent iodine-mediated intramolecular alkene halocyclisation

  • Charu Bansal,
  • Oliver Ruggles,
  • Albert C. Rowett and
  • Alastair J. J. Lennox

Beilstein J. Org. Chem. 2024, 20, 3113–3133, doi:10.3762/bjoc.20.258

Graphical Abstract
  • is then attacked by a nucleophile. The use of chiral iodine catalysts is essential for controlling the stereochemistry of the reaction. The specific arrangement of the catalyst influences the orientation of this nucleophilic attack as supported by density functional theory (DFT) calculations. In 2022
  • up to 95% within a short time-frame of 10 minutes. Treatment of N-(2-phenylallyl)benzamides with 10 equivalents of BF3·Et2O, iodobenzene, m-CPBA in dichloromethane (DCM) at 0 °C resulted in the formation of the oxazoline product (Scheme 21). DFT calculations indicated several steps in the mechanism
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Published 28 Nov 2024

Advances in the use of metal-free tetrapyrrolic macrocycles as catalysts

  • Mandeep K. Chahal

Beilstein J. Org. Chem. 2024, 20, 3085–3112, doi:10.3762/bjoc.20.257

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  • , with TBAI as a co-catalyst, up to 74% yields (Table 1). The inactivity of porphyrin 18 was attributed to the inaccessibility of the inner core imine due to its planar structure. The mechanism of the epoxide ring-opening reaction was elucidated by DFT calculations, which suggested that the macrocycle
  • (Table 5). DFT calculations predicted that the catalytically active species is the adduct of porphyrin and TBACl (18-I), which forms an activated complex (18-II) with the substrate followed by a ring-opening nucleophilic attack of Cl−. The electron-rich nitrogen atom in 18-III further activates
  • DFT studies to elucidate the mechanism of CO2 cycloaddition to aziridines using a metal-free protonated porphyrin macrocycle and found that the catalytic cycle started with simultaneous activation of both CO2 and N-butyl-2-phenylaziridine (69b). The main strategies used in metal-free porphyrin
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Published 27 Nov 2024

Enantioselective regiospecific addition of propargyltrichlorosilane to aldehydes catalyzed by biisoquinoline N,N’-dioxide

  • Noble Brako,
  • Sreerag Moorkkannur Narayanan,
  • Amber Burns,
  • Layla Auter,
  • Valentino Cesiliano,
  • Rajeev Prabhakar and
  • Norito Takenaka

Beilstein J. Org. Chem. 2024, 20, 3069–3076, doi:10.3762/bjoc.20.255

Graphical Abstract
  • in the absence and presence of N,N-diisopropylethylamine using density functional theory (DFT) calculations (Figure 1). According to the DFT calculations, the free propargyltrichlorosilane (Iprop) can isomerize to allenyltrichlorosilane (Iall) with a prohibitively high barrier of 43.8 kcal/mol
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Published 25 Nov 2024
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  • displayed the minus sign, whereas the acylated samples displayed the plus sign, and their plus-sign intensities increased in proportion to the length of the acyl chain (acetyl < propionyl < butyryl). These observations were consistent with the DFT-obtained simulated ICD spectra. Briefly, the minus Cotton
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Published 19 Nov 2024

Tailored charge-neutral self-assembled L2Zn2 container for taming oxalate

  • David Ocklenburg and
  • David Van Craen

Beilstein J. Org. Chem. 2024, 20, 3007–3015, doi:10.3762/bjoc.20.250

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  • sufficient quality to obtain a solid-state structure of the oxalate host–guest complex [(C2)@L2Zn2]2− so that we utilized DFT calculations to model the expected structure of the host–guest species (Figure 3a). Therefore, we funneled structural information obtained from NMR spectra into our starting geometry
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Published 18 Nov 2024

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

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  • approximately 150° [42][43][44][45]. These data were consistent with DFT calculations (see Supporting Information File 1). The reaction of the amide 1d with n-BuLi resulted in a surprising outcome. In this case, product 9d and only traces of the expected product 10d were received, as indicated by the 19F NMR
  • ]. These findings are in alignment with DFT calculations (see Supporting Information File 1) and corroborate data for compounds 9a–d. We further decided to use tert-BuLi in our research, considering its role as a stronger base and simultaneously as a weak nucleophile. We first performed the reaction with 2
  • remarkable stereoselectivity, a finding elucidated by DFT analysis. These results mark significant progress toward the synthesis of novel fluorinated building blocks. Our team is currently exploring the application of this methodology to amino acid substrates, aiming to contribute further to the burgeoning
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Published 15 Nov 2024

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

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  • the Knoevenagel condensation with malononitrile was successfully reported [33]. Theoretical studies Density functional theory (DFT) calculations of two derivatives of compounds 2 and 3, having methoxy groups instead of the longer alkyl chains have been reported in the literature [32], providing
  • hindered charge transport. Experimental Computational Density functional theory (DFT) calculations were performed using Gaussian 09 software. Molecular geometries were initially optimised semi-empirically (AM1) and then reoptimised by DFT using the B3LYP method with the 6-311G(d,p) basis set unless stated
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Published 13 Nov 2024

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
  • aryl sulfides 85 from thiols 84 using diaryliodonium salts 16 in basic conditions (Scheme 34). A multitude of thiols and diaryliodonium salts was examined in the reaction under optimized conditions, yielding exceptional yields [88]. To embrace the chemical process, DFT calculations were performed in
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Published 13 Nov 2024

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

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  • -β-41a (55%) and E-β-41a (41%) are in accordance with the relative thermodynamic stability of the two geometric isomers. According to DFT calculations, the Z-isomer is slightly energetically favored by 14.88 kJ/mol. The configurations were determined by comparison of chemical shifts of our products
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Published 08 Nov 2024

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

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  • ]pyrimidines using readily available derivatives of azaheterocycles as starting materials. As the last ones, we chose the reaction between 2-aminoimidazole and N-arylitaconimides or N-substituted maleimides, which can be analyzed by both classical synthetic and quantum DFT methods. The second problem solved in
  • 2 and 3, the minimum energy paths (MEPs) of these processes were calculated. Quantum chemical DFT calculations were performed using the B3LYP/6-311++G(d,p) basis set and taking into account solvation effects using the polarizable continuum model (PCM). Interactions of 1 with N-phenylmaleimide (2a
  • ). Conclusion Thus, we have proposed an efficient way to construct tetrahydroimidazo[1,2-a]pyrimidines without substituents at the 4 and 5-positions of the imidazole fragment by the reaction of 2-aminoimidazole with N-arylitaconimides and N-substituted maleimides. With the aid of DFT calculations, the most
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Published 05 Nov 2024

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

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  • ). Further control experiments and DFT calculations show that during the catalytic process, tertiary amine directly participates as a nucleophilic reagent to give the ammonium salt, which then releases dimethylaminium to provide the final product (Scheme 12). Chiral allylic sulfone compounds can be easily
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Published 31 Oct 2024

Deciphering the mechanism of γ-cyclodextrin’s hydrophobic cavity hydration: an integrated experimental and theoretical study

  • Stiliyana Pereva,
  • Stefan Dobrev,
  • Tsveta Sarafska,
  • Valya Nikolova,
  • Silvia Angelova,
  • Tony Spassov and
  • Todor Dudev

Beilstein J. Org. Chem. 2024, 20, 2635–2643, doi:10.3762/bjoc.20.221

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  • properties of γ-CD (the largest of the three most abundant native CDs), the main experimental methods applied in this study were differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). By coupling these techniques with density functional theory (DFT) calculations we try to shed some
  • of interactions (i.e., water–water and/or water–CD walls) contribute to the stability of the water assemble; (iv) how does the mechanism of the γ-CD hydration compare with those of its α-CD and β-CD counterparts. Keywords: cyclodextrin; DFT calculation; DSC/TG; hydration; thermodynamic
  • the γ-CD cavity, i.e., what is the saturation point of the γ-CD internal hydration as determined by DFT modeling of possible γ-CD–nH2O complexes? In general, the gas-phase calculations at the two levels of theory (and in aqueous media at the M062X/6-31G(d,p) level) show that the sequential insertion
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Published 17 Oct 2024

Anion-dependent ion-pairing assemblies of triazatriangulenium cation that interferes with stacking structures

  • Yohei Haketa,
  • Takuma Matsuda and
  • Hiromitsu Maeda

Beilstein J. Org. Chem. 2024, 20, 2567–2576, doi:10.3762/bjoc.20.215

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  • ]. In each structure, the non-hydrogen atoms were refined anisotropically. CIF files (CCDC-2364292–2364296) can be obtained free of charge from the Cambridge Crystallographic Data Centre via https://www.ccdc.cam.ac.uk/data_request/cif. DFT calculations. DFT calculations for the geometrical optimizations
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Published 10 Oct 2024

Machine learning-guided strategies for reaction conditions design and optimization

  • Lung-Yi Chen and
  • Yi-Pei Li

Beilstein J. Org. Chem. 2024, 20, 2476–2492, doi:10.3762/bjoc.20.212

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  • of molecules using density functional theory (DFT) calculations, which are computationally expensive and time-consuming [62]. To overcome this challenge, some studies have proposed to pre-generate QM properties datasets and train ML models to serve as fast feature generators for new molecules [16
  • ]. However, this approach requires careful validation of the training data coverage and the extrapolation ability of the surrogate models. Reaction-level descriptors based on DFT calculations of the TS structures of chemical reactions can provide valuable insights for predicting rate constants [113][114][115
  • solvent effects may complicate the results [122]. Therefore, reaction-level DFT-based descriptors are not widely used for reaction featurization. A more popular alternative is the differential reaction fingerprint (DRFP) developed by Probst et al. [123], which converts a reaction SMILES sequence into a
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Published 04 Oct 2024

Hypervalent iodine-mediated cyclization of bishomoallylamides to prolinols

  • Smaher E. Butt,
  • Konrad Kepski,
  • Jean-Marc Sotiropoulos and
  • Wesley J. Moran

Beilstein J. Org. Chem. 2024, 20, 2455–2460, doi:10.3762/bjoc.20.209

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  • the alkene and the amide increased from two to three atoms. In the latter case, cyclization at the amide nitrogen to form the pyrrolidine ring was favored over cyclization at the amide oxygen. A DFT study was undertaken to rationalize the change in mechanism of this cyclization process. In addition
  • , reaction conditions were developed, and the scope of this cyclization studied. Keywords: cyclization; DFT; hypervalent iodine; mechanism; proline; Introduction Proline is one of the 20 DNA-encoded proteinogenic amino acids that are essential to life [1][2]. In addition, the pyrrolidine core is present in
  • was the five-membered prolinol 7a rather than the initially assigned isomeric seven-membered tetrahydrooxazepine 6 [16]. Subsequently, we set out to understand the O- versus N-chemoselectivity by DFT modelling, and to develop an effective synthetic protocol for the preparation of prolinols 7 in high
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Published 30 Sep 2024

Synthesis and conformational analysis of pyran inter-halide analogues of ᴅ-talose

  • Olivier Lessard,
  • Mathilde Grosset-Magagne,
  • Paul A. Johnson and
  • Denis Giguère

Beilstein J. Org. Chem. 2024, 20, 2442–2454, doi:10.3762/bjoc.20.208

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  • and nonbonding interactions for the halogen at C4. Finally, density functional theory (DFT) calculations corroborate the preference of talose analogues to adopt a 4C1-like conformation and a natural bonding orbital (NBO) analysis demonstrates the effects of hyperconjugation from C–F antibonding
  • ) [24]. The solution and the solid-state conformational analysis were supplemented with DFT calculations to understand key conformational drivers. This study adds more data to the field of nuclear magnetic resonance (NMR) spectroscopy of polyhalogenated molecules. It should be noted that the NMR
  • -halides motivated us to use density functional theory (DFT) calculations to understand the preference of talose analogues to adopt 4C1-like conformations. DFT computations were performed using Gaussian 16 revision B.01 [67] with the CAM-B3LYP [68][69][70] functional and the Def2TZVP basis set [71], which
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Published 27 Sep 2024
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