Divergent role of PIDA and PIFA in the AlX₃ (X = Cl, Br) halogenation of 2-naphthol: a mechanistic study

• Kevin A. Juárez-Ornelas,
• Manuel Solís-Hernández,
• Pedro Navarro-Santos,
• J. Oscar C. Jiménez-Halla and
• César R. Solorio-Alvarado

Beilstein J. Org. Chem. 2024, 20, 1580–1589, doi:10.3762/bjoc.20.141

• , and transition-state structures were optimized by density functional theory (DFT) calculations employing the software Gaussian 16 [34]. Although the B3LYP functional could be suitable for these calculations, e.g., for tracing reaction pathways, nitrations, halogenations, or FC acylations in solution

Regio- and stereochemical stability induced by anomeric and gauche effects in difluorinated pyrrolidines

• Ana Flávia Candida Silva,
• Francisco A. Martins and
• Matheus P. Freitas

Beilstein J. Org. Chem. 2024, 20, 1572–1579, doi:10.3762/bjoc.20.140

• (nN→σ*CF anomeric and σCH→σ*CF fluorine gauche effects) on the conformation of different stereoisomers is explored. MAE comparing the geometry parameters (bond length, bond angle, and dihedral angle) obtained from DFT calculations at the CCSD/DGTZVP level. The MAE for the crystal structure compared to

Predicting bond dissociation energies of cyclic hypervalent halogen reagents using DFT calculations and graph attention network model

• Yingbo Shao,
• Zhiyuan Ren,
• Zhihui Han,
• Li Chen,
• Yao Li and
• Xiao-Song Xue

Beilstein J. Org. Chem. 2024, 20, 1444–1452, doi:10.3762/bjoc.20.127

• DFT calculations for predicting key properties of organic molecules such as BDE, nucleophilicity, and electrophilicity [48][49][50][51][52][53][54][55][56][57][58][59][60]. Recently, applications of the Elastic Net model with Avalon fingerprints [55] and the deployment of artificial neural network

Synthesis of cyclic β-1,6-oligosaccharides from glucosamine monomers by electrochemical polyglycosylation

• Md Azadur Rahman,
• Hirofumi Endo,
• Takashi Yamamoto,
• Shoma Okushiba,
• Norihiko Sasaki and
• Toshiki Nokami

Beilstein J. Org. Chem. 2024, 20, 1421–1427, doi:10.3762/bjoc.20.124

• DFT calculations in Supporting Information File 1). Therefore, it was proven that the 2,3-oxazolidinone protecting group was powerful enough to prevent intramolecular glycosylation of monomer 14. However, it did not prevent intramolecular glycosylation of the linear disaccharide and promote the

• monomers 6 with a 2-PhthN group. Electrochemical polyglycosylation of monomers 17 with a 2-azido group. Supporting Information Supporting Information File 18: Synthetic details, DFT calculations, and compound characterization data. Acknowledgements We thank Koganei Corporation (Tokyo, Japan) for donation

Computation-guided scaffold exploration of 2E,6E-1,10-trans/cis-eunicellanes

• Zining Li,
• Sana Jindani,
• Volga Kojasoy,
• Teresa Ortega,
• Erin M. Marshall,
• Khalil A. Abboud,
• Sandra Loesgen,
• Dean J. Tantillo and
• Jeffrey D. Rudolf

Beilstein J. Org. Chem. 2024, 20, 1320–1326, doi:10.3762/bjoc.20.115

• rearrangement; DFT calculations; diterpene; electrophilic cyclization; eunicellane; Introduction The eunicellane diterpenoids are a family of nearly 400 natural products that present a conserved 6/10-bicyclic hydrocarbon framework [1][2][3]. Mostly known from soft corals [2], but with a growing number of

• anticipated that 1 would similarly undergo Cope rearrangement. However, when we heated 1 up to 200 °C for 5 h, we did not observe any Cope rearrangement products and we were able to recover >90% of 1. DFT calculations [mPW1PW91/6–31+G(d/p)/SMD(toluene)] on the Cope rearrangement of 2 revealed a free energy

• activation energy may allow for oxy-Cope rearrangement at 28 °C. DFT calculations (in toluene) of 5-hydroxyalbireticulene for both the pseudo-axial and pseudo-equatorial conformations of the C5 hydroxy moiety suggest that there is not a significant difference in the free energy barriers for the oxy-Cope

Sustainable tandem acylation/Diels–Alder reaction toward versatile tricyclic epoxyisoindole-7-carboxylic acids in renewable green solvents

• Ayhan Yıldırım

Beilstein J. Org. Chem. 2024, 20, 1308–1319, doi:10.3762/bjoc.20.114

• (Figure 3, path I) [132]. Similarly, Tomberg et al., note that in such reactions, amide is formed rapidly by opening the maleic anhydride ring first, followed by a slower cyclization [133]. On the other hand, according to the results of some DFT calculations, Naguib et al., state that [4 + 2

Synthesis and physical properties of tunable aryl alkyl ionic liquids based on 1-aryl-4,5-dimethylimidazolium cations

• Stefan Fritsch and
• Thomas Strassner

Beilstein J. Org. Chem. 2024, 20, 1278–1285, doi:10.3762/bjoc.20.110

• start at 0 V. Structures of the imidazolium cations obtained by DFT calculations (B3LYP/6-311++G (d,p)). The electrostatic potentials are indicated by color (blue: positive; red: negative). Overview of the synthesis of compounds 1–63. Thermal decomposition point at 5% mass loss in °C for NTf2− TAAILs 37

Synthesis and optical properties of bis- and tris-alkynyl-2-trifluoromethylquinolines

• Stefan Jopp,
• Franziska Spruner von Mertz,
• Peter Ehlers,
• Alexander Villinger and
• Peter Langer

Beilstein J. Org. Chem. 2024, 20, 1246–1255, doi:10.3762/bjoc.20.107

• different fine structures. However, TD-DFT calculations using the long-range correlated CAM-B3LYP/6-311G(d,p) level of theory reveal that the lowest energy band for all three derivatives 6a, 9a and 12a originate mainly from a HOMO→LUMO transition with some admixture of HOMO−1→LUMO+1 and HOMO−1→LUMO

Competing electrophilic substitution and oxidative polymerization of arylamines with selenium dioxide

• Vishnu Selladurai and
• Selvakumar Karuthapandi

Beilstein J. Org. Chem. 2024, 20, 1221–1235, doi:10.3762/bjoc.20.105

• with arylamines follows a complex reaction pathway, leading to a mixture of compounds. We established the possible reaction pathways using 77Se NMR spectroscopy and single-crystal X-ray crystallographic studies. Density functional theory (DFT) calculations were carried out to understand the relative

• interactions are rarely reported and currently gaining interest [59]. Computational studies To comprehend the role of electron-donating and -withdrawing groups in arylamine oxidation using SeO2 as oxidant, DFT calculations were carried out on the arylamines and SeO2 using Gaussian 16 [60]. The molecular

Stability trends in carbocation intermediates stemming from germacrene A and hedycaryol

• Naziha Tarannam,
• Prashant Kumar Gupta,
• Shani Zev and
• Dan Thomas Major

Beilstein J. Org. Chem. 2024, 20, 1189–1197, doi:10.3762/bjoc.20.101

• reaction trajectory towards this pathway and make sure that it stays along this pathway and does not rearrange to a similar, more stable carbocation. Here, using density functional theory (DFT) calculations, we provide a rationale for the relative stability of the intermediate carbocations formed from

Two-fold addition reaction of silylene to C₆₀: structural and electronic properties of a bis-adduct

• Masahiro Kako,
• Masato Kai,
• Masanori Yasui,
• Michio Yamada,
• Yutaka Maeda and
• Takeshi Akasaka

Beilstein J. Org. Chem. 2024, 20, 1179–1188, doi:10.3762/bjoc.20.100

• silirane (silacyclopropane) derivative of fullerenes. Electrochemical measurements confirmed that the redox potentials of 3 are shifted cathodically compared to those of the parent mono-adduct 2. Density functional theory (DFT) calculations provided the basis for the electronic properties of compound 3

• results. To obtain some insight into regioselectivity, we performed density functional theory (DFT) calculations using the B3LYP/6-31G(d) method [45][46][47][48]. We first compared the relative stabilities of mono-adducts (Dip2SiC60) with 6,6-silirane (2a), 6,6-sila-fulleroid (2b), 5,6-silirane (2c), and

• spectroscopic and crystallographic analyses established 3 as an e isomer of bis-adducts with silirane structures at the 6,6-bonds. In the DFT calculations of mono-adduct 2a, the LUMO is distributed remarkably around the e’ bonds, which are likely to interact with the HOMO of 1 leading to the formation of 3

Manganese-catalyzed C–C and C–N bond formation with alcohols via borrowing hydrogen or hydrogen auto-transfer

• Mohd Farhan Ansari,
• Atul Kumar Maurya,
• Abhishek Kumar and
• Saravanakumar Elangovan

Beilstein J. Org. Chem. 2024, 20, 1111–1166, doi:10.3762/bjoc.20.98

• polyethyleneimine derivatives by coupling ethylene glycol and ethylenediamine using manganese-pincer catalyst Mn1 (1 mol %), t-BuOK (10 mol %) in toluene at 150 °C (Scheme 21) [48]. The mechanistic investigation based on the experimental and DFT calculations suggested a BH pathway. First, dehydrogenation of the

• amount of t-BuOK (20 mol %) in t-AmOH at 135 °C for 24 h allowed for the investigation of several alkyl and aryl ketones with amines and vicinal diols yielding good to excellent yields of the desired pyrroles (Scheme 70) with water and hydrogen gas being the only byproducts. DFT calculations suggested

Kinetically stabilized 1,3-diarylisobenzofurans and the possibility of preparing large, persistent isoacenofurans with unusually small HOMO–LUMO gaps

• Qian Liu and
• Glen P. Miller

Beilstein J. Org. Chem. 2024, 20, 1099–1110, doi:10.3762/bjoc.20.97

• Qian Liu Glen P. Miller Department of Chemistry, University of New Hampshire, 23 Academic Way, Durham, New Hampshire 03864-3598, USA 10.3762/bjoc.20.97 Abstract DFT calculations demonstrate that an isoacenofuran of any size possesses a smaller HOMO–LUMO gap than the corresponding acene bearing an

• utilized DFT calculations to demonstrate that isoacenofurans of any size possess smaller HOMO–LUMO gaps than the corresponding acene bearing an isoelectronic π-system. This finding alone provides compelling reasons to attempt the synthesis of large, persistent isoacenofurans for use as organic

Structure–property relationships in dicyanopyrazinoquinoxalines and their hydrogen-bonding-capable dihydropyrazinoquinoxalinedione derivatives

• Tural N. Akhmedov,
• Ajeet Kumar,
• Daken J. Starkenburg,
• Kyle J. Chesney,
• Khalil A. Abboud,
• Novruz G. Akhmedov,
• Jiangeng Xue and
• Ronald K. Castellano

Beilstein J. Org. Chem. 2024, 20, 1037–1052, doi:10.3762/bjoc.20.92

• to estimate energies of the frontier molecular orbitals (FMOs), specifically the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), for DCPQs 1a–7a as well as 1b–7b. The density functional theory (DFT) calculations were performed using the B3LYP/6-31+G

• . 13.0.0.3015 for Windows. The ground state geometries, energies and orbital energies were then obtained from DFT calculations at the B3LYP/6-31+G* level as implemented in Gaussian 09 [38], accessed through the UF High-Performance Computing Center. Frequency calculations were performed at the same computational

Evaluation of the enantioselectivity of new chiral ligands based on imidazolidin-4-one derivatives

• Jan Bartáček,
• Karel Chlumský,
• Jan Mrkvička,
• Lucie Paloušová,
• Miloš Sedlák and
• Pavel Drabina

Beilstein J. Org. Chem. 2024, 20, 684–691, doi:10.3762/bjoc.20.62

• tridentate chiral ligands: PyBOX [15] and PyBidine [16]. Additionally, we explored further modifications by substituting the pyridine moiety with an imidazole ring in ligand III (Figure 1), motivated by DFT calculations (see Supporting Information File 1, part S4) which confirmed that imidazole has a similar

• catalysed by copper(II) complex of ligand IV. Asymmetric aldol reactions of various aldehydes with ketones catalysed by compound IV. Supporting Information Supporting Information File 62: General information and experimental data of prepared compounds, copies of 1H and 13C NMR spectra and DFT calculations

Enhanced reactivity of Li⁺@C₆₀ toward thermal [2 + 2] cycloaddition by encapsulated Li⁺ Lewis acid

• Hiroshi Ueno,
• Yu Yamazaki,
• Hiroshi Okada,
• Fuminori Misaizu,
• Ken Kokubo and
• Hidehiro Sakurai

Beilstein J. Org. Chem. 2024, 20, 653–660, doi:10.3762/bjoc.20.58

• of this straightforward and selective reaction for Li+@C60. Results and Discussion We began by performing density functional theory (DFT) calculations to screen the substrates with suitable HOMO levels for the thermal [2 + 2] cycloaddition with Li+@C60. The structures of several kinds of possible

Enhanced host–guest interaction between [10]cycloparaphenylene ([10]CPP) and [5]CPP by cationic charges

• Eiichi Kayahara,
• Yoshiyuki Mizuhata and
• Shigeru Yamago

Beilstein J. Org. Chem. 2024, 20, 436–444, doi:10.3762/bjoc.20.38

• photophysical and electrochemical analyses and DFT calculations. Therefore, this CT is most likely the origin of the increased Ka value. We also discuss the charged double-layer structure, as determined by X-ray crystallographic analysis. Results and Discussion The size-complementary interaction between CPP2

• absorption bands in the visible region and characteristic broad absorption bands extending to the NIR region (≈2000 nm) (Figure 4, black line). According to time-dependent density functional theory (DFT) calculations at the ωB97-XD/6-31G* level of theory, the NIR absorption of the most thermodynamically

• transition corresponds to the CT band. The structure and stability of [10]CPP⊃[5]CPP2+ were estimated by DFT calculations at the ωB97-XD/6-31G* level of theory. Three isomeric structures were optimized, of which complex 1, with two CPPs aligned in parallel, is the most thermodynamically stable (Figure 5a

Facile approach to N,O,S-heteropentacycles via condensation of sterically crowded 3H-phenoxazin-3-one with ortho-substituted anilines

• Eugeny Ivakhnenko,
• Vasily Malay,
• Pavel Knyazev,
• Nikita Merezhko,
• Nadezhda Makarova,
• Oleg Demidov,
• Gennady Borodkin,
• Andrey Starikov and
• Vladimir Minkin

Beilstein J. Org. Chem. 2024, 20, 336–345, doi:10.3762/bjoc.20.34

• –H proton. Therefore, three tautomeric forms are possible for 5 (Scheme 4), one of which, the 7H-tautomer 7b, inevitably adopts a bipolar or biradical structure. According to the data from the DFT calculations performed at the B3LYP/6-311++G(d,p) approximation (Figure S6, Supporting Information File

• reaction products as 12H-quinoxaline[2,3-b]phenoxazines was confirmed through DFT calculations, X-ray crystallography, and NMR spectroscopy. Electronic absorption spectra (Table 2 and Figures 5–7) and electrochemical properties (Table 3) of the heteropentacyclic compounds 4a–h, 5a–c, 6a,b, and 10c revealed

• ). The DFT calculations [32] were performed using the Gaussian 16 program package [33] with the B3LYP functional [34] and the 6-311++G(d,p) basis set. The structures corresponding to minima on the potential energy surface and states with broken symmetry [20] were found through complete optimization of

Unveiling the regioselectivity of rhodium(I)-catalyzed [2 + 2 + 2] cycloaddition reactions for open-cage C₇₀ production

• Cristina Castanyer,
• Anna Pla-Quintana,
• Anna Roglans,
• Albert Artigas and
• Miquel Solà

Beilstein J. Org. Chem. 2024, 20, 272–279, doi:10.3762/bjoc.20.28

• opening. Keywords: cycloadditions; DFT calculations; [70]fullerene; open-cage fullerenes; rhodium; Introduction The discovery of C60 (buckminsterfullerene) in 1985 [1] initiated the search for possible technological applications of fullerenes. Nowadays, applications for these carbon-based molecules have

• in both cases. This preference was rationalized by means of DFT calculations. Moreover, the photooxidation of one of the C–C double bonds of the new bis(fulleroids) afford open-cage C70 derivatives having a 12-membered ring opening. It is noteworthy to mention that examples of open-cage C70

Photochromic derivatives of indigo: historical overview of development, challenges and applications

• Gökhan Kaplan,
• Zeynel Seferoğlu and
• Daria V. Berdnikova

Beilstein J. Org. Chem. 2024, 20, 228–242, doi:10.3762/bjoc.20.23

• '-dinitrobenzoylindigo 18b were provided by de Melo and co-workers in 2020 using modern femtosecond spectroscopic techniques as well as TD-DFT calculations [60]. In 1989, Takahashi and co-workers reported an important study of geometry and conformational stability of indigo and its N,N'-disubstituted derivatives [61][62

Perspectives on push–pull chromophores derived from click-type [2 + 2] cycloaddition–retroelectrocyclization reactions of electron-rich alkynes and electron-deficient alkenes

• Michio Yamada

Beilstein J. Org. Chem. 2024, 20, 125–154, doi:10.3762/bjoc.20.13

• . The absolute configurations of the axially chiral TCBD and DCNQ derivatives were ascertained by a comparative analysis of the experimental CD spectra against the spectra derived from time-dependent density functional theory (TD-DFT) calculations. The axial chirality was stabilized by the steric

Electron-beam-promoted fullerene dimerization in nanotubes: insights from DFT computations

• Laura Abella,
• Gerard Novell-Leruth,
• Josep M. Ricart,
• Josep M. Poblet and
• Antonio Rodríguez-Fortea

Beilstein J. Org. Chem. 2024, 20, 92–100, doi:10.3762/bjoc.20.10

• pressures and high temperatures [13][14][15]. We aim to shed light in these reaction mechanisms and energy profiles by using complementary methodologies as standard density functional theory (DFT) calculations and first-principles Car–Parrinello molecular dynamics (CPMD) simulations. Firstly, we have

Beyond n-dopants for organic semiconductors: use of bibenzo[d]imidazoles in UV-promoted dehalogenation reactions of organic halides

• Kan Tang,
• Megan R. Brown,
• Chad Risko,
• Melissa K. Gish,
• Garry Rumbles,
• Phuc H. Pham,
• Oana R. Luca,
• Stephen Barlow and
• Seth R. Marder

Beilstein J. Org. Chem. 2023, 19, 1912–1922, doi:10.3762/bjoc.19.142

• weak shoulder at ca. 400 nm (ε400 ≈ 150 M−1 cm−1), whereas (Cyc-DMBI)2 exhibits only a strong feature with a maximum at 327 nm (εmax = 13000 M−1 cm−1). TD-DFT calculations (M06/6-31G(d,p), isolated molecules) qualitatively reproduce the different behavior of the two dimers: for (Cyc-DMBI)2 the S0→S1

• longer-time spectra with Cyc-DMBI• having a blue-shifted absorption relative to N-DMBI•, consistent with the observed features arising from the monomeric radicals. Intersystem crossing (ISC) from the singlet to triplet excited state is also a possibility and TD-DFT calculations suggest that the dimer T1

• toluene, and (c) (Cyc-DMBI)2 in toluene with excitation at 350 nm in the absence of oxygen. (d) Comparison of temporal evolution of the absorption at 654 nm for both dimers in toluene. (e) Spectra for the two monomeric radicals obtained from M06/6-31G(d,p) TD-DFT calculations. Selective deiodination of 2

Thienothiophene-based organic light-emitting diode: synthesis, photophysical properties and application

• Recep Isci and
• Turan Ozturk

Beilstein J. Org. Chem. 2023, 19, 1849–1857, doi:10.3762/bjoc.19.137

• . The high thermal stability is profitable for the preparation of stable and durable OLED devices. Computational chemistry Ground-state geometry optimization of DMB-TT-TPA (8) was performed using density functional theory (DFT) calculations with the Gaussian 16 software at the B3LYP/6-31G (d,p) level

• and TT units, the LUMO was found to be delocalized through the dimesitylboron and TT ring, the results being in line with the experimental values of our previous study [23]. On the basis of the optimized ground-state geometry, time-dependent DFT (TD-DFT) calculations were conducted in THF to

• computation data, 1H and 13C NMR spectra. Acknowledgements The authors thank Dilara Gunturkun for DFT calculations, Istanbul Technical University (ITU). Funding The authors thank THD-2023-44904, PTA-2023-44900, TGA-2023-44077, TDA-2022-43696 numbered ITU BAP Projects and 122Z568 numbered TUBITAK 1001 Project

Recent advancements in iodide/phosphine-mediated photoredox radical reactions

• Tinglan Liu,
• Yu Zhou,
• Junhong Tang and
• Chengming Wang

Beilstein J. Org. Chem. 2023, 19, 1785–1803, doi:10.3762/bjoc.19.131

• esters 8, 9 without the requirements of phosphine or other photocatalysts (Scheme 5). Through the use of density functional theory (DFT) calculations, they elucidated the mechanism behind this process. It was revealed that the formation of a photoactive EDA complex, which subsequently generated alkyl