Catalytic asymmetric reactions of isocyanides for constructing non-central chirality

• Jia-Yu Liao

Beilstein J. Org. Chem. 2025, 21, 1648–1660, doi:10.3762/bjoc.21.129

• of phenyl iodide to Pd(0) to generate the phenyl Pd(II) species. After that, coordination and migratory insertion of the first isocyanide group of 16a to Pd(II) delivered INT-I. Then, coordination and migratory insertion of the second isocyanide group occurred to give INT-III, which underwent

• distortion of isocyanoacetate–Ag coordination combing with better Ag–C σ-orbital overlap led to exo-cycloadducts (L10-TS). Except for constructing C–N and N–N axial chirality, we have developed a highly diastereo- and enantioselective method to access tri- and tetra-ortho-substituted biaryl aldehydes 63

On the aromaticity and photophysics of 1-arylbenzo[a]imidazo[5,1,2-cd]indolizines as bicolor fluorescent molecules for barium tagging in the study of double-beta decay of ¹³⁶Xe

• Eric Iván Velazco-Cabral,
• Fernando Auria-Luna,
• Juan Molina-Canteras,
• Miguel A. Vázquez,
• Iván Rivilla and
• Fernando P. Cossío

Beilstein J. Org. Chem. 2025, 21, 1627–1638, doi:10.3762/bjoc.21.126

• decoupling between the para-phenylene and benzo[a]imidazo[5,1,2-cd]indolizine components that results in a blue shift upon Ba2+ coordination. Keywords: aromaticity; DFT-TDDFT calculations; double-beta decay; fluorescent sensors; polycyclic arenes; Introduction Double beta-decay [1] is a radioactive decay

• possible. The role of the crown ether and the para-phenylene moieties was also analyzed. The interactions of different sized crown ethers with Ba2+ and coordination with the aromatic ring modeled by means of benzene (14, highlighted in yellow in Scheme 2) were studied computationally. Although the

• , highlighted by an asterisk, lies out from the direct coordination perimeter, thus suggesting that this ligand is too big. The relatively lower increase of the ΔGiso(d) with respect to its ΔGiso(c) congener also indicate that the stabilization induced by the additional oxygen atom is lower in magnitude. An

3-Aryl-2H-azirines as annulation reagents in the Ni(II)-catalyzed synthesis of 1H-benzo[4,5]thieno[3,2-b]pyrroles

• Julia I. Pavlenko,
• Pavel A. Sakharov,
• Anastasiya V. Agafonova,
• Derenik A. Isadzhanyan,
• Alexander F. Khlebnikov and
• Mikhail S. Novikov

Beilstein J. Org. Chem. 2025, 21, 1595–1602, doi:10.3762/bjoc.21.123

• -catalyzed reaction proceeds with low diastereoselectivity. The significant difference in selectivity can be explained by the fact that, in contrast to the Ni(II)-catalyzed reaction depicted in Scheme 3, the copper(I) catalysis involves the coordination by the metal of both reaction partners, and the

• formation of the C–C bond between the rings of the reacting molecules occurs in the coordination metal sphere as an intra-, rather than intermolecular, process. The formation of compound 17, the product of oxidative dimerization of indole-based enol 15, in the second reaction also points to different

Ambident reactivity of enolizable 5-mercapto-1H-tetrazoles in trapping reactions with in situ-generated thiocarbonyl S-methanides derived from sterically crowded cycloaliphatic thioketones

• Grzegorz Mlostoń,
• Małgorzata Celeda,
• Marcin Palusiak,
• Heinz Heimgartner,
• Marta Denel-Bobrowska and
• Agnieszka B. Olejniczak

Beilstein J. Org. Chem. 2025, 21, 1508–1519, doi:10.3762/bjoc.21.113

• cyclobutanones, which are easily accessible via desulfurization reaction of the thiiranes described in the present study (via the Barton–Kellogg reaction [38][39]). This type of ethylenic compounds is of interest, e.g., for structural, coordination and materials chemistry, as well [39][40][41][42][43]. Moreover

Microwave-enhanced additive-free C–H amination of benzoxazoles catalysed by supported copper

• Andrei Paraschiv,
• Valentina Maruzzo,
• Filippo Pettazzi,
• Stefano Magliocco,
• Paolo Inaudi,
• Daria Brambilla,
• Gloria Berlier,
• Giancarlo Cravotto and
• Katia Martina

Beilstein J. Org. Chem. 2025, 21, 1462–1476, doi:10.3762/bjoc.21.108

• also required to obtain a pure final product. To overcome this problem, a heterogeneous catalytic approach has been developed in which copper is anchored on an aminated silica support. Given that ammonia, amino derivatives and other nitrogen-containing compounds form strong coordination complexes with

Advances in nitrogen-containing helicenes: synthesis, chiroptical properties, and optoelectronic applications

• Meng Qiu,
• Jing Du,
• Nai-Te Yao,
• Xin-Yue Wang and
• Han-Yuan Gong

Beilstein J. Org. Chem. 2025, 21, 1422–1453, doi:10.3762/bjoc.21.106

• nm) attributed to reversible intramolecular charge transfer [20]. In parallel, several groups explored the functional versatility of heterohelicenes in device-oriented and sensing applications. Crassous’s group synthesized bipyridine-embedded helicenes via the Mallory reaction, enabling coordination

• value of 0.28. Upon coordination with tris(4-bromophenyl)aminium hexachloroantimonate (BAHA), a new absorption band emerged around 900 nm, extending to 1300 nm, indicative of charge-transfer processes. The enantiomers of 13 displayed mirror-image CD signals and showed excellent dispersibility in polar

• -containing hetero[7]helicene 36a containing a boron–nitrogen coordination site [50]. Its chiroptical properties could be modulated through the addition of tetrabutylammonium (TBA) salts, which transformed the boron center from a trigonal planar to a tetrahedral geometry, thereby enhancing the |glum| from 4.7

Oxetanes: formation, reactivity and total syntheses of natural products

• Peter Gabko,
• Martin Kalník and
• Maroš Bella

Beilstein J. Org. Chem. 2025, 21, 1324–1373, doi:10.3762/bjoc.21.101

• epoxide-opening cyclisation for the oxetane formation (Scheme 11b) [45]. The highest yield was obtained for the PhSH/I2 10:1 activator under unusually mild conditions – the authors believed it is due to the oxa-bridge which facilitates the Lewis acid coordination. In 2001, Rousseau and colleagues reported

Recent advances in oxidative radical difunctionalization of N-arylacrylamides enabled by carbon radical reagents

• Jiangfei Chen,
• Yi-Lin Qu,
• Ming Yuan,
• Xiang-Mei Wu,
• Heng-Pei Jiang,
• Ying Fu and
• Shengrong Guo

Beilstein J. Org. Chem. 2025, 21, 1207–1271, doi:10.3762/bjoc.21.98

Enhancing chemical synthesis planning: automated quantum mechanics-based regioselectivity prediction for C–H activation with directing groups

• Julius Seumer,
• Nicolai Ree and
• Jan H. Jensen

Beilstein J. Org. Chem. 2025, 21, 1171–1182, doi:10.3762/bjoc.21.94

• directing group facilitates this step as it stabilizes the complex through coordination to the Pd atom, thereby lowering the reaction barrier. A depiction of the CMD step is shown in Figure 1. Upon C–H bond breaking, the Pd atom moves into the plane of the aromatic ring, forming a palladacycle intermediate

Gold extraction at the molecular level using α- and β-cyclodextrins

• Susana Santos Braga

Beilstein J. Org. Chem. 2025, 21, 1116–1125, doi:10.3762/bjoc.21.89

• organometallics guests, albeit less common, are also observed. These form a variety of structures from supramolecular second-sphere coordination adducts to pseudorotaxanes [35][36]. With highly charged metal ions, electrostatic interactions and first-sphere coordination bonds are dominant, while second-sphere

• coordination with inorganic and organometallic complexes involves hydrophobic interactions and van der Waals forces (mainly with the organic parts of these guests). Several forces are at play in the formation of supramolecular assemblies with gold in the form of haloaurate ions, as detailed in the forthcoming

• cations, the geometry is different from that observed in {α-CD·[K(OH2)6]+[AuBr4]−}n, because coordination of Rb+ and Cs+ takes place both at OH groups and at the O atoms of the glucopyranosyl ring in the CD tori (Figure 2, right). This strong coordination, in cooperation with the geometrically favourable

Supramolecular assembly of hypervalent iodine macrocycles and alkali metals

• Krishna Pandey,
• Lucas X. Orton,
• Grayson Venus,
• Waseem A. Hussain,
• Toby Woods,
• Lichang Wang and
• Kyle N. Plunkett

Beilstein J. Org. Chem. 2025, 21, 1095–1103, doi:10.3762/bjoc.21.87

• are presented. Keywords: hypervalent iodine; macrocycle; metal coordination; supramolecular; Introduction Supramolecular chemistry is emerging as a pivotal area of research in both medicinal and materials chemistry that opens the avenue for new functionalized materials for their use in medical

• Information File 1. Single crystals with quality suitable for XRD analysis were obtained in both cases (Figure 5). Unlike the previous assumption of metal coordination at the macrocycle core [17], the crystal structures reveal complexation of both cations at the periphery of the macrocycle. Both 1/LiBArF20

• in this HIM system, the 1H NMR titration data was used to determine the association constants for metal coordination. Two stock solutions were prepared with one containing a concentration of 2.83 mM of the macrocycle (HIM) in a mixture of deuterated chloroform and acetone 1:2. The second stock

Recent advances in synthetic approaches for bioactive cinnamic acid derivatives

• Betty A. Kustiana,
• Galuh Widiyarti and
• Teni Ernawati

Beilstein J. Org. Chem. 2025, 21, 1031–1086, doi:10.3762/bjoc.21.85

On the photoluminescence in triarylmethyl-centered mono-, di-, and multiradicals

• Daniel Straub,
• Markus Gross,
• Mona E. Arnold,
• Julia Zolg and
• Alexander J. C. Kuehne

Beilstein J. Org. Chem. 2025, 21, 964–998, doi:10.3762/bjoc.21.80

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

• studied silver(I)-catalyzed intramolecular heteroannulation reaction is depicted in Scheme 5. The process begins with the π-coordination of the silver catalyst to the triple bond in the Ugi-adduct 15a generating intermediate A. This is followed by a nucleophilic attack by the pyrazole nitrogen on the

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

• , enabling programmable access to structurally distinct molecular architectures from identical substrate precursors through precise manipulation of metal coordination [16][17][18]. This sophisticated approach capitalizes on the stereoelectronic tunability of ancillary ligands to dictate reaction pathways

• , tetrabutylammonium iodide (TBAI), and water significantly accelerated aryne generation, thereby increasing its local concentration. This favored aryne coordination to the palladium center, followed by CO insertion and reductive elimination to furnish phenanthridinones. In contrast, when dppm was introduced

• , oxidative addition of the C–I bond to palladium formed the four-membered aryl–palladium complex Int-5. Steric hindrance from the bulky dppm ligand, combined with slower aryne release (using KF as the fluoride source), attenuated aryne coordination. Under these electron-deficient conditions, CO

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

• mechanism for the copper-catalyzed diastereoselective dimerization of 4,4-dichoro-2-butenoic acid derivatives (Scheme 4). Initially, the LCu–pin complex generated through reaction between LCu–Ot-Bu and B2pin2 undergoes coordination and regioselective insertion into 1 giving rise to β-borylated organocopper

• addition to a second molecule of 1. Given the negative results observed for other crotonate derivatives (Scheme 3c), coordination between the Li cation and the two chlorine atoms via proposed transition state D may be crucial not only for diastereoselective control but also for the viability of this step

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

• L as an anion receptor to extract cesium salts (chloride, nitrate, carbonate, sulfate, and phosphate) from the solid phase into chloroform. Remarkably, Cs3PO4 exhibits the highest extraction efficiency, driven by strong cooperative interactions involving ion-dipole coordination between Cs+ and

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

• classical azobenzenes. Heterocyclic rings offer, for example, enhanced polarity, electron pairs for metal coordination [27], better water-solubility, and variable pKa [28][29]. Special attention has been given to 5-membered N-heterocyclic azobenzenes, which not only maintain the azobenzenes properties but

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

• . Trimethylsilyl cyanide (TMSCN) has been used as a sacrificial cyanide source. We found that isocyanide (rather than cyanide) is a preferred coordination to calcium during the catalytic cycle, while the active catalyst prefers a side-on coordination of cyanide. The configuration-determining step is a

• conditions. The product was isolated as colorless crystals in good yield of 81% (Scheme 1). Complex 4 crystallizes as a C2-symmetric chiral mononuclear complex in which Ca is bound to two monodentate phosphate ligands (Figure 1). Four MeOH ligands complete the slightly distorted octahedral coordination

• 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

Recent advances in allylation of chiral secondary alkylcopper species

• Minjae Kim,
• Gwanggyun Kim,
• Doyoon Kim,
• Jun Hee Lee and
• Seung Hwan Cho

Beilstein J. Org. Chem. 2025, 21, 639–658, doi:10.3762/bjoc.21.51

• interactions and enhanced electronic stabilization through lithium coordination. This explains the critical role of lithium in achieving a high enantioselectivity. Isotope-labeling experiments using 10B-enriched 1,1-diborylalkanes (S)-49 further supported this mechanism, showing a stereoinvertive

• energy compared to (S,S)-TS9. Both transition states demonstrated a lithium center's coordination involving bromide, benzoate, and ligand oxygen atoms. The (S,R)-TS8 transition state exhibited a significantly shorter Li–Br interaction distance (2.81 Å compared to 3.74 Å in (S,S)-TS9), offering

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

• reacts with the enolate of the ketone, which is stabilized by coordination with Fe(III), resulting in the formation of the C–C bond. A further oxidative aromatization process affords compound I. Compared to the protocol developed by Zhang et al. [24], the reaction is less regioselective, as Troger’s base

Photomechanochemistry: harnessing mechanical forces to enhance photochemical reactions

• Francesco Mele,
• Ana M. Constantin,
• Andrea Porcheddu,
• Raimondo Maggi,
• Giovanni Maestri,
• Nicola Della Ca’ and
• Luca Capaldo

Beilstein J. Org. Chem. 2025, 21, 458–472, doi:10.3762/bjoc.21.33

• zinc cations to align 1.1 through the formation of hydrogen-bonded coordination complexes. Thus, when a single crystal of the [Zn(bpe)2(H2O)4](NO3)2·8/3H2O·2/3bpe complex was exposed to UV irradiation (dark blue phosphor lamps, λ = 350 nm) for 25 h, only 46% conversion to 1.2 was observed via 1H NMR

Electrochemical synthesis of cyclic biaryl λ³-bromanes from 2,2’-dibromobiphenyls

• Andrejs Savkins and
• Igors Sokolovs

Beilstein J. Org. Chem. 2025, 21, 451–457, doi:10.3762/bjoc.21.32

• starts with a single-electron oxidation of 4a on the electrode surface to form cation radical A, in which Br(II) is chelation-stabilized by the carboxyl group [21] and the neighbouring Br substituent [24]. Intermediate A rapidly undergoes irreversible chemical reaction by HFIP coordination to transient

Beyond symmetric self-assembly and effective molarity: unlocking functional enzyme mimics with robust organic cages

• Keith G. Andrews

Beilstein J. Org. Chem. 2025, 21, 421–443, doi:10.3762/bjoc.21.30

• proximal electrostatic potential, even when the charges are flexibly arranged, remote, and solvated in water. Metal-organic cages The exploration of metal-organic cages (MOCs), also known as supramolecular coordination cages (SCCs), as catalysts is thriving [22][36][138][139][140][141]. The reversible bond

• typically not possible for imine [314] or metal-coordination cages [156][202][365]. Further, the robust amide cages could withstand harsh conditions such as ester hydrolysis, allowing access to the key acid-functionalized cages [38] that mimic aspartyl proteases and glycoside hydrolases. Otte has employed

• between a simple, highly symmetrical, often hydrophobic pocket of a typical coordination cage host system and the complex, highly unsymmetrical and largely polar environment of an enzyme active site is a moot point… [since]… the mechanisms which an enzyme utilizes to accelerate chemical reactions are in

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

• compounds 5a, 5b, 6b, 6c, and 7a. Acknowledgements The physicochemical studies were performed on the equipment of Center for Collective Use ''Physical and chemical methods for the study of nitro compounds, coordination, biologically active substances and nanostructured materials'' at the Interdisciplinary