Study of tribenzo[b,d,f]azepine as donor in D–A photocatalysts

• Katy Medrano-Uribe,
• Jorge Humbrías-Martín and
• Luca Dell’Amico

Beilstein J. Org. Chem. 2025, 21, 935–944, doi:10.3762/bjoc.21.76

• of D–A structures makes them the ideal structures to further understand the structure–property relationship of D–A molecules for optimizing their photocatalytic performance by simpler modification of the different D–A subunits. In particular, D–A structures featuring sulfur-based acceptors and

• is a particular interest in the obtainment of organic molecules with well-balanced redox potentials in the excited state that can act as bimodal photocatalysts, facilitating their use in oxidative and reductive quenching cycles. In this sense, it is crucial to understand the molecule's structure

• –properties dependence to modulate its optical and photoredox properties [4]. For instance, molecules with donor–acceptor (D–A) structures, classically used as OLED emitters, have gained relevance by finding alternative applications in the field of photocatalysis [5]. In this type of structure, the electron

A convergent synthetic approach to the tetracyclic core framework of khayanolide-type limonoids

• Zhiyang Zhang,
• Jialei Hu,
• Hanfeng Ding,
• Li Zhang and
• Peirong Rao

Beilstein J. Org. Chem. 2025, 21, 926–934, doi:10.3762/bjoc.21.75

• their total synthesis. Two synthetic studies were disclosed successively by Sarpong [27] and Jirgensons [28], both focusing on the construction of the unique methanoindene cage structure (A1A2B ring system). Building upon our previous syntheses of phragmalin-type limonoids [29], we herein disclose a

• 11 in the presence of AcOH by exposure to UV-light at 254 nm occurred exclusively to provide an inseparable mixture of 32 and 33 (Table 1, entry 5). Subsequent dehydration of the resultant mixture with SOCl2 and pyridine yielded separable enones 34 (51%) and 10 (9%) over two steps. The structure of

• ). Construction of α-iodoenone 13. Construction of aldehyde 14. Synthesis of the advanced intermediate 10 (in the X ray structure of 10 solvent molecule is omitted for clarity). Optimization of the interrupted Nazarov cyclization.a Supporting Information Deposition number 2406738 contains the supplementary

Silver(I) triflate-catalyzed post-Ugi synthesis of pyrazolodiazepines

• Muhammad Hasan,
• Anatoly A. Peshkov,
• Syed Anis Ali Shah,
• Andrey Belyaev,
• Chang-Keun Lim,
• Shunyi Wang and
• Vsevolod A. Peshkov

Beilstein J. Org. Chem. 2025, 21, 915–925, doi:10.3762/bjoc.21.74

• trifluoromethyl and nitro groups. Furthermore, substrates 15m–o derived from aliphatic amines, also performed well, furnishing pyrazolodiazepines 16m–o in up to 89% yield. The structure of 16m, a representative compound of this series, was confirmed through single-crystal X-ray diffraction (scXRD) analysis

Recent advances in controllable/divergent synthesis

• Jilei Cao,
• Leiyang Bai and
• Xuefeng Jiang

Beilstein J. Org. Chem. 2025, 21, 890–914, doi:10.3762/bjoc.21.73

• protoberberine and protonitidine alkaloids are characterized by an isoquinoline ring skeleton. An analysis of their molecular structures revealed that the two alkaloids share a basic structure, differing only in the junction of the B-ring. In 2021, Liu and Jiang designed new pyridyne precursors, which underwent

• discussion emphasizes structure–reactivity relationships and catalytic design principles that enable predictable access to distinct molecular architectures from shared synthetic intermediates. This review serves as a conceptualized platform for controllable/divergent synthesis, arousing more state-of-the-art

Dicarboxylate recognition based on ultracycle hosts through cooperative hydrogen bonding and anion–π interactions

• Wen-Hui Mi,
• Teng-Yu Huang,
• Xu-Dong Wang,
• Yu-Fei Ao,
• Qi-Qiang Wang and
• De-Xian Wang

Beilstein J. Org. Chem. 2025, 21, 884–889, doi:10.3762/bjoc.21.72

• binding sites to enhance anion binding [30]. The recognition capabilities of these ultracycles toward a range of dicarboxylates were successfully demonstrated. Results and Discussion Synthesis and structure The ultracycles B4aH, B5aH, and B6aH were synthesized following the previously reported procedure

• hydrogen bonding and anion–π interactions between the host and guest, we carried out geometry optimizations using M06-2X at the 6-31G(d) level of theory, taking the [B4aH·C72−] complex as a representative example [35][36]. The optimized structure, shown in Figure 3, reveals a 1:1 complex in which the

• interactions, the host undergoes conformational adjustments: the distance between the two submacrocycles increases, and the glycol chains adopt extended conformations compared to the structure shown in Figure 1. These results suggest that the experimentally observed strong binding capability and selectivity of

Cu–Bpin-mediated dimerization of 4,4-dichloro-2-butenoic acid derivatives enables the synthesis of densely functionalized cyclopropanes

• Patricia Gómez-Roibás,
• Andrea Chaves-Pouso and
• Martín Fañanás-Mastral

Beilstein J. Org. Chem. 2025, 21, 877–883, doi:10.3762/bjoc.21.71

• organoboron compound with CuOt-Bu and subsequent SN2’-selective allylic alkylation of 1. The densely functionalized structure of these dimerization products offers a versatile synthetic handle for further chemoselective functionalization. Considering the presence of two enolizable esters together with the

• of the twofold utility of KOt-Bu, we explored the formation of this new cyclopropane structure directly from gem-dichloride 5. By using this base under standard conditions, product 20 was selectively obtained in similar yield, albeit with diminished diastereoselectivity (Scheme 5b). Conclusion In

Data accessibility in the chemical sciences: an analysis of recent practice in organic chemistry journals

• Sally Bloodworth,
• Cerys Willoughby and
• Simon J. Coles

Beilstein J. Org. Chem. 2025, 21, 864–876, doi:10.3762/bjoc.21.70

• data guidance. We suggest first steps that researchers can take to move towards a positive culture of data sharing in organic chemistry. Routine actions that we encourage as standard practice include deposition of raw and metadata to open repositories, and inclusion of machine-readable structure

• from the ‘all data’ group which combines the other categories, because an excellent data culture is already established for crystallographic data publishing. All journals expect CIF validation using accessible tools (checkCIF [34] or enCIFer [35]), and deposition of CIF files and structure factor

• tables with the Cambridge Crystallographic Data Centre (CCDC), enabling full access to the contained structure information via the CSD repository. For other data types, 11 of the 12 journal titles recommend that primary data are deposited in a repository and encourage authors to consider FAIR data

Light-enabled intramolecular [2 + 2] cycloaddition via photoactivation of simple alkenylboronic esters

• Lewis McGhie,
• Hannah M. Kortman,
• Jenna Rumpf,
• Peter H. Seeberger and
• John J. Molloy

Beilstein J. Org. Chem. 2025, 21, 854–863, doi:10.3762/bjoc.21.69

• + 2] cycloaddition established, the scope and pivotal properties of the core structure was assessed (Scheme 1). Single point modifications of the tethered backbone were tolerated, enabling access to small 3D bicyclic scaffolds 4b, 4c, and 4d containing both a boron and ester handle. Consciously aware

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

• -pairing) could be enhanced along with the charge of the anion and its binding affinity with L (from Cl– to CO32–, and PO43–). Notably, for the first time, direct ion-pairing between receptor-complexed phosphate and 18-crown-6 complexed cesium was observed in the single crystal structure, facilitating

• interaction in nonpolar solvent could be stronger than that in polar solvent [45][46][47][48]. The ion-dipole interaction between complexed Cs+ cation and receptor–sulfate complex was first identified by single crystal structure analysis (Figure 2). The overall stoichiometry of L, 18-crown-6, Cs+, and SO42

• − was 4:5:4:2 in the crystalized structure. Like the structure of K2SO4 complexes [31], one Cs+ cation is encapsulated by 18-crown-6 and further stabilized by one ion-dipole interaction with the O=C unit of the hexaurea receptor. The Cs···O distance is measured at 3.2 Å. The other two Cs+ cations are

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

• -art technologies ranging from energy-storage materials [6][7] to pharmacology [8][9][10][11], materials chemistry [12][13], control of peptides structure [14][15] or proteins [16], as antibacterial agents [17][18], smart coating [19], or multivalent photoresponsive systems [20][21], to name only a few

• 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

• spectroscopy, the structure of 4-(1-methylamino)ethylidene-1,5-diphenylpyrrolidine-2,3-dione (5a) was also verified through single-crystal X-ray diffraction. Furthermore, the synthesized molecules were evaluated for compliance with established drug-likeness rules (Lipinski, Veber, Ghose, Egan, and Muegge), as

• -pyrroline-2-ones 1a–e and 4-methoxybenzylamine (2) in absolute ethanol yielded 4-[1-(4-methoxybenzyl)amino]ethylidene-1,5-disubstituted pyrrolidine-2,3-diones 3a–e (Scheme 1) [19][20][21]. In addition to nuclear magnetic resonance spectroscopy (1D, 2D NMR), the structure of 3a has also been proven via

• -hybridized carbon atom directly bonded to the nitrogen atom of the secondary amino group of compound 5a. In the structure of each pyrrolidine-2,3-dione derivative 3a–e, there is an α,β-unsaturated ketone moiety in which the π systems of the C=C and C=O bonds could overlap each other to yield an extended

Synthesis and photoinduced switching properties of C₇-heteroatom containing push–pull norbornadiene derivatives

• Daniel Krappmann and
• Andreas Hirsch

Beilstein J. Org. Chem. 2025, 21, 807–816, doi:10.3762/bjoc.21.64

• Bansal and co-workers [44] revealed the potential formation of aza-QC derivatives at low temperatures. However, isolation of these derivatives proved difficult, as rapid rearrangement to azepine analogues occurred at temperatures exceeding 0 °C. On the basis of the quadricyclane or azepine structure

• described a variety of potential rearrangements for oxa-NBD and oxa-QC derivatives [32][34][36][37]. Therefore, in-depth 2D NMR analysis combined with mass spectrometry was attempted to elucidate the structure of O-UnS2. Notably, an additional singlet proton signal (integrated as 1 proton) corresponding to

• the unidentified species was observed, which cannot be present in the structure of O-QC2. Further irradiation over 18 hours resulted in additional rearrangements or photodecomposition, which were not analyzed further. At slightly lower concentrations (5.0 mg substance in 650 μL CDCl3) quantitative

Recent advances in the electrochemical synthesis of organophosphorus compounds

• Babak Kaboudin,
• Milad Behroozi,
• Sepideh Sadighi and
• Fatemeh Asgharzadeh

Beilstein J. Org. Chem. 2025, 21, 770–797, doi:10.3762/bjoc.21.61

• exhibited higher stability compared to 4d and 5d transition metals. Through the study of a series of previous experiments, it was shown that the electron density of the nitrogen atom in the quinoline structure significantly affects the efficiency of nickel-electrocatalysis; however, other N,N- or N,O

• and the overall structure of the complex highly influence the oxidation potential of Pd(II). At first, a complex of phenylpyridine with palladium (including insertion of Pd to C–H bond) and dialkyl phosphonate was formed, followed by anodic oxidation to give the final coupling product. In 2023, Zhou

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

• sphere. The phosphate ligands are in cis-position with respect to each other. The structure of 4 shows similarities to that of a BINOL-derived calcium phosphate complex that also crystallizes with four methanol ligands, creating an octahedral coordination sphere with phosphate ligands in cis-position [52

• ]. As observed earlier [53], cis/trans preferences in octahedral calcium complexes are influenced by small changes in sterics. Further details on the structure of 4 can be found in Supporting Information File 1. Complex 4 appeared to be a well-defined achiral model system for the catalyst combination

• later stages of the catalytic cycle, are less likely to racemize without bond breaking. The barrier to pyramidal inversion has been found to be 15.1 kcal·mol−1. Berry rotation itself proceeds via a tetragonal pyramid as transition-state structure and does therefore not occur here. A second isocyanide

Orthogonal photoswitching of heterobivalent azobenzene glycoclusters: the effect of glycoligand orientation in bacterial adhesion

• Leon M. Friedrich and
• Thisbe K. Lindhorst

Beilstein J. Org. Chem. 2025, 21, 736–748, doi:10.3762/bjoc.21.57

• periphery of the FimH form the basis of the higher FimH affinity of the E isomers (as was argued in similar case [15]) (cf. Supporting Information File 1, Figure S25 and Figure S26). A possible allosteric regulation of the CRD structure [55][56], on the other hand, which might be effected by one of the

Synthesis of HBC fluorophores with an electrophilic handle for covalent attachment to Pepper RNA

• Raphael Bereiter and
• Ronald Micura

Beilstein J. Org. Chem. 2025, 21, 727–735, doi:10.3762/bjoc.21.56

• fluorophore derivatives bind the Pepper aptamer with affinities in the low nanomolar range [12]. Crystal structure analyses revealed that in the ligand binding pocket, a characteristic hydrogen bond is formed between the hydroxy group of the N-hydroxyethyl substituent of HBC and the N7 of G41 [12][13]. We

• . HPLC traces were recorded with UV absorption by 260 nm. Structure-guided approach for engineering the (non-covalent) fluorescent light-up aptamer Pepper into its covalent counterpart [11]. a) Secondary structure of the Pepper aptamer [12]; b) chemical structure of the fluorophore HBC530 [7]; c) three

• -dimensional structure of the Pepper binding site with a bound HBC derivative (pdb code 7EOM). The hydrogen bond between N7 of guanine in position 41 (G41) and the hydroxy group of HBC is highlighted as gray dashed line [12]; d) concept for covalent attachment of HBC fluorophores to the N7 atom of G41 of the

Acyclic cucurbit[n]uril bearing alkyl sulfate ionic groups

• Christian Akakpo,
• Peter Y. Zavalij and
• Lyle Isaacs

Beilstein J. Org. Chem. 2025, 21, 717–726, doi:10.3762/bjoc.21.55

• alkyl sulfate ionic groups. The X-ray crystal structure of the C1·Me6CHDA complex is reported. Host C1 is significantly less soluble in water (4 mM) compared to the analogous acyclic CB[n] host M1 which features sulfonate ionic groups (346 mM). Host C1 does not undergo significant self-association

• are acyclic CB[n]-type receptors which have been extensively studied by our lab and others over the past decade [42][43][44][45][46][47][48][49][50][51][52]. Figure 1 shows the chemical structure of the prototypical acyclic CB[n]-type known as M1 [53][54]. M1 features a central glycoluril tetramer

• acyclic CB[n] are not macrocycles, they are preorganized into a C-shaped geometry by virtue of their polycyclic chemical structure and display binding affinities approaching those of macrocyclic CB[n]. M1 and analogues display outstanding biocompatibility and have been used for a number of in vivo

Origami with small molecules: exploiting the C–F bond as a conformational tool

• Patrick Ryan,
• Ramsha Iftikhar and
• Luke Hunter

Beilstein J. Org. Chem. 2025, 21, 680–716, doi:10.3762/bjoc.21.54

• fluorine atoms into the structure. The C–F bond has certain fundamental characteristics that enable it to serve as an effective conformational tool (Figure 1) [2][3][4]. First, the C–F bond is quite short at only ≈1.35 Å (cf. ≈1.09 Å for C–H, or ≈1.43 Å for C–O). The short length of the C–F bond, and the

• attached to every carbon of an alkyl chain (e.g., II, Figure 4), then a structure results that is conceptually intermediate between alkanes and perfluoroalkanes. Such structures, dubbed “multivicinal fluoroalkanes”, have interesting conformational properties that are dependent upon the stereochemistry [39

• ubiquitous molecules in biology. Their functions permeate every aspect of life, including as essential components of oligonucleotide structure; as principal players in metabolism and energy storage; as motifs for the post-translational modification of proteins; and as partners in myriad supramolecular

Photochemically assisted synthesis of phenacenes fluorinated at the terminal benzene rings and their electronic spectra

• Yuuki Ishii,
• Minoru Yamaji,
• Fumito Tani,
• Kenta Goto,
• Yoshihiro Kubozono and
• Hideki Okamoto

Beilstein J. Org. Chem. 2025, 21, 670–679, doi:10.3762/bjoc.21.53

• serves as a p-channel organic semiconductor [37], whereas perfluoropentacene can be used as an n-channel material [38]. It has been demonstrated that the molecular structure of [7]helicenes was modified by fluorination, thus, the helicenes’ pitch was manipulated by terminal fluorination modes [39][40

• homologue structure, there was a significant contribution from the H–L transition in the α band, presumably because of the difference in the molecular symmetry. Conclusion Octafluorinated phenacenes, F8PIC, F8FUL, and F87PHEN, were conveniently synthesized through the Mallory photoreaction as the key step

Asymmetric synthesis of fluorinated derivatives of aromatic and γ-branched amino acids via a chiral Ni(II) complex

• Maurizio Iannuzzi,
• Thomas Hohmann,
• Michael Dyrks,
• Kilian Haoues,
• Katarzyna Salamon-Krokosz and
• Beate Koksch

Beilstein J. Org. Chem. 2025, 21, 659–669, doi:10.3762/bjoc.21.52

• , which have yet to be described in the context of peptide chemistry. The several CF3 groups employ a strong inductive effect on the aromatic ring structure, making these amino acids highly interesting building blocks for modification of aromatic–aromatic interactions in the context of protein folding

Entry to 2-aminoprolines via electrochemical decarboxylative amidation of N‑acetylamino malonic acid monoesters

• Olesja Koleda,
• Janis Sadauskis,
• Darja Antonenko,
• Edvards Janis Treijs,
• Raivis Davis Steberis and
• Edgars Suna

Beilstein J. Org. Chem. 2025, 21, 630–638, doi:10.3762/bjoc.21.50

• feature at Ep = 1.78 V vs Ag/Ag+ (100 mV/s scan rate; see Figure 3A), and the electrolysis of pyrrolidine 6a under the optimized anodic decarboxylative cyclization conditions (entry 8, Table 1) afforded cyclic hemiaminal 12a (33% NMR yield), whose structure was proved by NMR experiments (Figure 3B). The

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

• such methods are generally reported with a heterogeneous DAR, the group developed a site-specific approach leading to a homogeneous DAR 2, thanks to a photoreactive Fc-binding peptide derivative (pFcBP) containing a photoleucine (pLeu) [46]. By analyzing the X-ray crystal structure of IgG, the

• intermediates can lead to protein denaturation or aggregation [61]. Because photoredox reactions often generate highly reactive species (such as radicals or singlet oxygen), long exposure times could cause unwanted side reactions, including the degradation of 3D structure of the protein or antibody. A short

Semisynthetic derivatives of massarilactone D with cytotoxic and nematicidal activities

• Rémy B. Teponno,
• Sara R. Noumeur and
• Marc Stadler

Beilstein J. Org. Chem. 2025, 21, 607–615, doi:10.3762/bjoc.21.48

• , 4.4 Hz) and H-4 (δH 4.38, dd, J = 4.3, 0.9 Hz, H-4), the trans-2-methyl-2-butenoyl moiety was placed at C-7. The above spectroscopic data combined to the analysis of 2D experiments led to the elucidation of the structure of compound 6 as massarilactone D 7-O-trans-2-methyl-2-butenoyl. The reaction of

• cytotoxic activity of natural products by increasing the hydrophobicity, enhancing cell membrane permeability and binding affinity with intracellular targets [26]. Structure–activity relationships analysis of both hemisynthetic products 2 and 3 revealed a shared conjugated methylene olefinic function that

• , as indicated by structure–activity relationship analysis. Conclusion In the present study, the use of various acylating reagents to modify massarilactone D introduces distinct functional groups, each with unique chemical properties. This approach led to the synthesis of seven previously undescribed

Total synthesis of (±)-simonsol C using dearomatization as key reaction under acidic conditions

• Xiao-Yang Bi,
• Xiao-Shuai Yang,
• Shan-Shan Chen,
• Jia-Jun Sui,
• Zhao-Nan Cai,
• Yong-Ming Chuan and
• Hong-Bo Qin

Beilstein J. Org. Chem. 2025, 21, 601–606, doi:10.3762/bjoc.21.47

• , including insecticidal, antibacterial, anti-inflammatory, analgesic, and neurotrophic activities [3]. In 2013, Wang’s group isolated (±)-simonsol C from star anise, which features a unique 6/5/6 tricyclic benzofuran structure [4]. They found that it exhibits biological activity that promotes neuronal

• oxy-Michael addition from dienone 15. The 6/6/6 tricyclic structure in 15 can be constructed through dearomatization of compound 16, which in turn can be readily synthesized through consecutive alkylation steps starting from magnolol (11). Additionally, using magnolol as the starting material brings

Formaldehyde surrogates in multicomponent reactions

• Cecilia I. Attorresi,
• Javier A. Ramírez and
• Bernhard Westermann

Beilstein J. Org. Chem. 2025, 21, 564–595, doi:10.3762/bjoc.21.45

• first reacts with the aniline under cobalt(III) catalysis, and the resulting intermediate C then attacks the thionium ion A. Quinolines of general structure II are formed after the loss of methyl sulfide from intermediate D, followed by final cyclization of intermediate E (Scheme 8, path II

• various substitution patterns in the aromatic ring, allowing a high variety of quinolines of general structure I and II. In a related work, quinolines of structure I (Scheme 8) could be obtained by similar reaction pathways. Jadhav et al. proposed a three-component cascade reaction between anilines

• was carried out via copper catalysis or iodine–acid catalysis. Interestingly, when aliphatic amines are employed (R3 = n-Pr, n-Bu, product 8) only the N atoms are incorporated in the structure of the final product, probably because the high temperature favors the elimination of the alkyl group. The