Synthesis of new condensed naphthoquinone, pyran and pyrimidine furancarboxylates

• Kirill A. Gomonov,
• Vasilii V. Pelipko,
• Igor A. Litvinov,
• Ilya A. Pilipenko,
• Anna M. Stepanova,
• Nikolai A. Lapatin,
• Ruslan I. Baichurin and
• Sergei V. Makarenko

Beilstein J. Org. Chem. 2025, 21, 340–347, doi:10.3762/bjoc.21.24

• atoms were refined in anisotropic approximation. The hydrogen atoms were placed in calculated positions and refined according to the rider model. The figures were performed in the Mercury 2020.3 program [38], the analysis of intermolecular contacts was performed according to the PLATON program [39]. The

Red light excitation: illuminating photocatalysis in a new spectrum

• Lucas Fortier,
• Corentin Lefebvre and
• Norbert Hoffmann

Beilstein J. Org. Chem. 2025, 21, 296–326, doi:10.3762/bjoc.21.22

• transformations have been addressed by Gianetti et al. such as C(sp3)–H oxidation, intermolecular atom transfer radical addition and C(sp)–H arylation using red light and DMQA (Figure 14), hence showing the great versatility of this photocatalyst. Red-light photocatalysis in biological systems Photochemical

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

• ] reported a stable heptacene dication in concentrated sulfuric acid, a stability attributed to the intermolecular Coulomb repulsion between the charged molecules, which prevents the dimerization of the acene. This exciting finding suggests possible modes of kinetic stabilization of oxidized species of π

Heteroannulations of cyanoacetamide-based MCR scaffolds utilizing formamide

• Marios Zingiridis,
• Danae Papachristodoulou,
• Despoina Menegaki,
• Konstantinos G. Froudas and
• Constantinos G. Neochoritis

Beilstein J. Org. Chem. 2025, 21, 217–225, doi:10.3762/bjoc.21.13

• was observed at an average wavelength of 384 nm for 5a–e, 439 nm for 6a–e and 430 nm for 7a–e (see Supporting Information File 1 for detailed information). In support of the proposed scaffold 7b, we were able to solve its crystal structure (Figure 3). An intermolecular bifurcated hydrogen bond network

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

• intermolecular forces, collectively, may also play a role. This proposal is further supported by the weaker linear relationship between ΔGexp and ELP→σ* (Figure 6E and Figure S46 in Supporting Information File 1). Collectively, these results indicate that the ΔδDMSO–CDCl3 or ΔδDMSO–CD3NO2 measurement can

Hydrogen-bonded macrocycle-mediated dimerization for orthogonal supramolecular polymerization

• Wentao Yu,
• Zhiyao Yang,
• Chengkan Yu,
• Xiaowei Li and
• Lihua Yuan

Beilstein J. Org. Chem. 2025, 21, 179–188, doi:10.3762/bjoc.21.10

• cooperative intermolecular forces. Zinc ion-induced coordination with the macrocycle and a terpyridinium derivative enabled orthogonal polymerization, as revealed by 1H NMR, DLS, and TEM techniques. In addition, viscosity measurements showed a transition from oligomers to polymers at the critical

• , including pyridinium and its derivatives [40]. More importantly, it favors intermolecular π-stacking interactions with aromatic guests [48]. Herein, we report on a novel supramolecular dimerization motif in 2:2 stoichiometry using H-bonded aramide macrocycles for constructing orthogonal supramolecular

• noncovalent interactions, particularly intermolecular π–π-stacking and C–H···O interactions. Specifically, π–π-stacking interactions were found between two guest molecules with aromatic rings arrayed in an offset fashion with a distance of 3.3 Å (Figure 3a). Interestingly, these interactions also existed

Cu(OTf)₂-catalyzed multicomponent reactions

• Sara Colombo,
• Camilla Loro,
• Egle M. Beccalli,
• Gianluigi Broggini and
• Marta Papis

Beilstein J. Org. Chem. 2025, 21, 122–145, doi:10.3762/bjoc.21.7

• -difunctionalization of alkenes carried out with carbazates (N-aminocarbamates) and (hetero)arene nucleophiles or amines exploiting N-(tert-butyl)-N-fluoro-3,5-bis(trifluoromethyl)benzenesulfonamide (NFBS) as intermolecular hydrogen-atom-transfer reagent results in alkylarylation processes (Scheme 5) [19]. The

• reaction proceeds through an initial single-electron transfer from NFBS assisted by the active copper species, followed by intermolecular hydrogen-atom transfer from the carbazate. The nitrogen radical intermediate I thus formed is decomposed into the acyl or alkyl radical intermediates II and III

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

• -67034 Strasbourg, France 10.3762/bjoc.20.270 Abstract The high potential of non-covalent arene–fluoroarene intermolecular interactions in the design of liquid crystals lies in their ability to strongly promote self-assembly, improve the order and stability of the supramolecular mesophases, and enable

• derivatives and the antiparallel stacking mode into columnar structures stabilized by arene–perfluoroarene intermolecular interactions were confirmed by the single-crystal structure of the alkoxy-free side chain analog, i.e., 1,2,4-trifluoro-3-(perfluorophenyl)triphenylene (F). UV–vis absorption and

• red-shift of the emission peak. Keywords: arene–perfluoroarene interaction; decafluorobiphenyl; fluorinated triphenylene; fluoroarene nucleophilic substitution; organolithium; Introduction Non-covalent arene–fluoroarene intermolecular interactions [1][2] are drawing increasing attention due to their

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

• , Mei and co-workers reported a chiral phosphoric acid-catalyzed asymmetric intermolecular formal (3 + 2) cycloaddition of azoalkenes 53 with azlactones 15 (Scheme 28). This methodology provides fully substituted 4-pyrrolin-2-ones 78 bearing a quaternary carbon atom in high yields (72–95%) and

• -Diels–Alder reaction of 1,3-diazadienes and 3-vinylindoles. Chiral phosphoric acid-catalyzed asymmetric Attanasi reaction between 1,3-dicarbonyl compounds and azoalkenes. Synthetic applicability of the NPNOL derivatives. Chiral phosphoric acid-catalyzed asymmetric intermolecular formal (3 + 2

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

• , including ligand coupling, oxidative addition, intermolecular nucleophilic attack, 1,2-aryl migration, reductive elimination, and intramolecular nucleophilic attack. This approach offers a rapid and effective way to produce 5-fluoro-2-aryloxazoline compounds, which are valuable building blocks in organic

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

• metalloporphyrins that are easily accessible for the incoming substrates, pyrrole –N/NH moieties inside the core of metal-free porphyrins are mostly hidden and unavailable for any kind of intermolecular hydrogen-bonding interactions or molecular recognition as they are 'shielded' by the planar macrocyclic system

Cyclodextrin-based rotaxanes for polymer materials: challenge on simultaneous realization of inexpensive production and defined structures

• Yosuke Akae

Beilstein J. Org. Chem. 2024, 20, 3026–3049, doi:10.3762/bjoc.20.252

Tunable full-color dual-state (solution and solid) emission of push–pull molecules containing the 1-pyrindane moiety

• Anastasia I. Ershova,
• Sergey V. Fedoseev,
• Konstantin V. Lipin,
• Mikhail Yu. Ievlev,
• Oleg E. Nasakin and
• Oleg V. Ershov

Beilstein J. Org. Chem. 2024, 20, 3016–3025, doi:10.3762/bjoc.20.251

• rigidity along the C–C bond between the heterocycle and ethene bridge due to the fused cyclic fragment. As a consequence of the additional ring, the fluorescence efficiency increased. At the same time, solid-state emission was observed due to the steric hindrance, which prevented intermolecular

• contrast to related compounds A (Figure 1), were characterized by solid-state emission (Table 4 and Figure 8). This was apparently caused by the presence of the dimethylene bridge, preventing intermolecular interactions. Emission maxima of compounds 1 ranged from 540–767 nm, namely from the green to the

Advances in radical peroxidation with hydroperoxides

• Oleg V. Bityukov,
• Pavel Yu. Serdyuchenko,
• Andrey S. Kirillov,
• Gennady I. Nikishin,
• Vera A. Vil’ and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2024, 20, 2959–3006, doi:10.3762/bjoc.20.249

• 22 (steps F, G). The third possible pathway involves the abstraction of a hydrogen atom from 4-hydroxy-2(5H)-furanone 21 by the tert-butoxy radical formed in step A to give the alkoxy radical III (step H). Intermolecular hydrogen atom transfer results in the C-centered radical IV (step I). Further

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

• , organic semiconductor molecules with large fused conjugated systems have achieved high charge carrier mobility. Such molecular structures improve the intermolecular interactions (such as π–π stacking) that are required to facilitate the hopping of charge carriers between adjacent molecules [7][8][9

• ][16][17], high electron affinity, excellent self-assembling properties [18][19][20], and thermal and photochemical stabilities [21]. The excellent charge carrier mobility of PDIs has been explained by the intermolecular π–π interactions with an interplanar distance (3.3–3.5 Å) [22][23][24][25] that

• intermolecular interactions which might result in a narrower HOMO–LUMO gap than that of PDI, and an absorption band extending to the near-infrared (NIR) region [26]. This makes violanthrone and its derivatives potential candidates for NIR optoelectronic applications. In fact, the intrinsic semiconducting

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

Mechanochemical difluoromethylations of ketones

• Jinbo Ke,
• Pit van Bonn and
• Carsten Bolm

Beilstein J. Org. Chem. 2024, 20, 2799–2805, doi:10.3762/bjoc.20.235

• with the generation of difluorocarbene from TMSCF2Br and KFHF. This is followed by a nucleophilic attack of the oxygen atom of ketone 1 on the difluorocarbene. Subsequently, a protonation–deprotonation sequence occurs, which can either be intermolecular, involving a molecule of HF, or intramolecular

• process. As a result, no H/D-exchange was detected. The experimental results of both experiments suggest that the reaction predominantly proceeds through an intermolecular pathway. The occurrence of the CF2D product may be attributed to a minor intramolecular reaction path or the involvement of DF formed

• isolating the low-boiling non-polar products. Mechanistic studies suggested that in situ-generated difluorocarbene reacts with the ketone oxygen, followed by intermolecular protonation/deprotonation. Although the process has still synthetic limitations, also acyclic ketones can now be converted into

C–C Coupling in sterically demanding porphyrin environments

• Liam Cribbin,
• Brendan Twamley,
• Nicolae Buga,
• John E. O’ Brien,
• Raphael Bühler,
• Roland A. Fischer and
• Mathias O. Senge

Beilstein J. Org. Chem. 2024, 20, 2784–2798, doi:10.3762/bjoc.20.234

• nanotubes/nanochannels by intermolecular π–π interactions of the peripheral phenyl groups [59]. Additionally nonplanar supramolecular assemblies have found use in anion capture [12][15], and sensing [60], making the synthesis of these structures desirable from a supramolecular standpoint. Two especially

Photoluminescence color-tuning with polymer-dispersed fluorescent films containing two fluorinated diphenylacetylene-type fluorophores

• Kazuki Kobayashi,
• Shigeyuki Yamada,
• Motohiro Yasui and
• Tsutomu Konno

Beilstein J. Org. Chem. 2024, 20, 2682–2690, doi:10.3762/bjoc.20.225

• . Judging from the fact that compounds 1a and 1c form a tight molecular packing via intermolecular H···F hydrogen bonds which suppress non-radiative deactivation in the crystalline state [20][21], we speculated that the polymer dispersion state had lost the intermolecular interactions, which accelerated the

Computational design for enantioselective CO₂ capture: asymmetric frustrated Lewis pairs in epoxide transformations

• Maxime Ferrer,
• Iñigo Iribarren,
• Tim Renningholtz,
• Ibon Alkorta and
• Cristina Trujillo

Beilstein J. Org. Chem. 2024, 20, 2668–2681, doi:10.3762/bjoc.20.224

• results, we looked into the literature to explore examples of asymmetric FLPs. This exploration revealed three main types, namely, intramolecular chiral FLPs, intermolecular FLPs composed of a chiral acid and an achiral base, and intermolecular FLPs comprising an achiral acid and a chiral base [61][62

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

• cyclodextrin cavity and in the intermolecular space. Several overlapped steps are visible on the TG curve, which is associated with the release of water molecules in several stages, with the steepest lightening of the sample at 350–370 K. Consistent with this is the DSC endothermic peak, which is asymmetric

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

• intermolecular C–H···π interactions between the proximally located CH3 and TATA+ units, as obtained by the Hirshfeld surface analysis (Figure 4) [33][34][35][36]. The arrangement of the ion pairs depended on the counteranions, which formed different interactions. Smaller counteranions were located above the

• the aid of intermolecular C–H···π interactions. Such characteristic anion-driven assemblies of TATA+ are not known, and further studies on ion-pairing assemblies of modified TATA+ can lead to the development of functional materials, comprising multiple components associated via iπ–iπ interactions that

A review of recent advances in electrochemical and photoelectrochemical late-stage functionalization classified by anodic oxidation, cathodic reduction, and paired electrolysis

• Nian Li,
• Ruzal Sitdikov,
• Ajit Prabhakar Kale,
• Joost Steverlynck,
• Bo Li and
• Magnus Rueping

Beilstein J. Org. Chem. 2024, 20, 2500–2566, doi:10.3762/bjoc.20.214

HFIP as a versatile solvent in resorcin[n]arene synthesis

• Hormoz Khosravi,
• Valeria Stevens and
• Raúl Hernández Sánchez

Beilstein J. Org. Chem. 2024, 20, 2469–2475, doi:10.3762/bjoc.20.211

• from intermolecular dehydration, nowadays known as alkyl resorcin[4]arene. Forty years later in 1980, Höegberg noticed that short alkyl chain resorcin[n]arenes develop stereoisomers in the reaction mixture; however, since the condensation reaction is reversible, once the macrocycle adopts the bowl

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

• provided slight improvements in yield (Table 1, entries 2–4). The more electron-rich 2-iodo-1,3-dimethoxybenzene led to a further increase in yield to 44% (Table 1, entry 5). 1,2-Diiodobenzene has been reported to be a superior precatalyst in intermolecular C–H aminations of arenes but only provided 40