Asymmetric synthesis of β-amino cyanoesters with contiguous tetrasubstituted carbon centers by halogen-bonding catalysis with chiral halonium salt

• Yasushi Yoshida,
• Maho Aono,
• Takashi Mino and
• Masami Sakamoto

Beilstein J. Org. Chem. 2025, 21, 547–555, doi:10.3762/bjoc.21.43

• organic chemistry [2][3][4][5], organocatalysis [6][7], metal catalysis [8][9], biochemistry [10][11], materials science [12][13], and supramolecular chemistry [14][15], although its successful application to asymmetric catalysis has been limited (Figure 1) [16][17][18][19][20]. In 2018, Arai and co

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

• surface area exposed to light but also to allow the motions within the crystal. In another instance, MacGillivray and colleagues reported the synthesis of rctt-tetrakis(4-pyridyl)cyclobutane (2.3) via [2 + 2] photodimerization of trans-1,2-bis(4-pyridyl)ethylene (2.1) via supramolecular catalysis by 4,6

• . Mechanochemically triggered pedal-like motion in solid-state [2 + 2] photochemical cycloaddition for the formation of cyclobutanes [62]. Mechanically promoted [2 + 2] photodimerization of trans-1,2-bis(4-pyridyl)ethylene (2.1) via supramolecular catalysis by 4,6-dichlororesorcinol (2.2) in the solid state [64

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

• Keith G. Andrews Department of Chemistry, Durham University, Lower Mount Joy, South Rd, Durham, DH1 3LE, UK 10.3762/bjoc.21.30 Abstract The bespoke environments in enzyme active sites can selectively accelerate chemical reactions by as much as 1019. Macromolecular and supramolecular chemists have

• symmetry to enable promising catalytic modes. Keywords: cavity confinement catalysis; enzyme mimicry; robust organic cages; self-assembly; supramolecular catalysis; Introduction I frequently introduce my research on organic cage enzyme mimics with the following observation. For hundreds of years

• -accelerations (1019) [1], tolerance of contaminants, and selectivity associated with the power of enzymes. It is for this reason that I have sought to introduce supramolecular approaches into my organocatalysis [2]. From thermodynamics, there are two components to catalysis: organization (entropic) and

Unraveling aromaticity: the dual worlds of pyrazole, pyrazoline, and 3D carborane

• Zahra Noori,
• Miquel Solà,
• Clara Viñas,
• Francesc Teixidor and
• Jordi Poater

Beilstein J. Org. Chem. 2025, 21, 412–420, doi:10.3762/bjoc.21.29

• chemistry [4][5][6]. Pyrazoles are also extensively employed in agrochemicals, serving as key components in insecticides, herbicides, and fungicides [7]. Beyond their chemical uses, pyrazoles play an important role in the construction of supramolecular assemblies and molecular systems designed for

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

• Wentao Yu Zhiyao Yang Chengkan Yu Xiaowei Li Lihua Yuan College of Chemistry, Sichuan University, Chengdu 610064, China 10.3762/bjoc.21.10 Abstract Orthogonal self-assembly represents a useful methodology to construct supramolecular polymers with AA- and AB-type monomers, as commonly used for

• effectively applied to form orthogonal supramolecular polymers. The macrocycle-mediated connectivity was confirmed by single-crystal X-ray diffraction, which revealed a unique 2:2 binding motif between host and guest, bridged by two cationic pyridinium end groups through π-stacking interactions and other

• polymerization concentration of 17 μM. These polymers were highly concentration-dependent. Establishing this new dimerization motif with shape-persistent H-bonded macrocycles widens the scope of noncovalent building blocks for supramolecular polymers and augurs well for the future development of functional

Hot shape transformation: the role of PSar dehydration in stomatocyte morphogenesis

• Remi Peters,
• Levy A. Charleston,
• Karinan van Eck,
• Teun van Berlo and
• Daniela A. Wilson

Beilstein J. Org. Chem. 2025, 21, 47–54, doi:10.3762/bjoc.21.5

• glutamate); polysarcosine; shape transformation; stomatocyte; supramolecular chemistry; Introduction Polymeric vesicles represent a promising candidate for usage in drug delivery systems due to their facile assembly and ability to provide a stable soft interface. Among these materials, polyethylene glycol

Synthesis of acenaphthylene-fused heteroarenes and polyoxygenated benzo[j]fluoranthenes via a Pd-catalyzed Suzuki–Miyaura/C–H arylation cascade

• Merve Yence,
• Dilgam Ahmadli,
• Damla Surmeli,
• Umut Mert Karacaoğlu,
• Sujit Pal and
• Yunus Emre Türkmen

Beilstein J. Org. Chem. 2024, 20, 3290–3298, doi:10.3762/bjoc.20.273

• focus of extensive research within the past two decades due to their interesting structural features, attractive photophysical properties, and diverse applications [2]. Indeed, fluoranthenes are particularly useful in supramolecular chemistry, organic electronics, and materials science [3] as

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

• critical role in the engineering of functional and complex supramolecular assemblies [3][4][5][6][7][8][9][10][11], ranging from rigid crystalline architectures [3][4][5][6][7][8] to soft liquid crystalline materials [9][10][11]. Their unique properties originate from the high electronegativity of the

• very similar, with no effect of the pending group nature (C6H5 vs C6F5) on the mesophase stability. A proposed model for the supramolecular organization of Fn in the Colhex phase is shown in Figure S42 of Supporting Information File 1. The bitriphenylene Gnm materials exhibit different X-ray patterns

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

• , porphyrins and corroles, which are structurally related to porphyrins. Calix[4]pyrroles are versatile receptors in supramolecular chemistry while porphyrins are considered as ‘pigment of life’ due to their role in vital biological processes. Beyond their natural functions, synthetic porphyrins have been

• conformational flexibility, allowing them to adopt four key conformations: 1,3-alternate, cone, partial cone, and 1,2-alternate [1][2]. Calix[4]pyrroles are one of the most studied hosts in supramolecular chemistry, finding use in applications of molecular recognition and extraction, drug delivery, ion transport

• recognition, and supramolecular assemblies [9][10][11][12][13]. There are numerous examples of using metalloporphyrins as artificial photosynthesis models, enzyme mimics, and catalysts for various organic transformations, where a metal center acts as an active site [14][15][16][17]. However, metal-free (or

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

• reaction via a simple process compared with other synthesis methods, this method can be developed as a platform for constructing rotaxane structures for further supramolecular-architecture designs, which will be explored in more detail. When a perfectly methylated α-CD (PMα-CD) is used for rotaxane

• named the vinylic supramolecular crosslinker (VSC), which was made of an axle component having a polymerizable vinylic group and a bulky end-capping group on the other side, and α-CD oligomer having around 3–5 α-CDs linked by a PPG linker with urethane bonds as the wheel component. This VSC was easily

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

• porphyrin architectures, which could be used in supramolecular assemblies, catalysis, or sensing. In this work a library of arm-extended dodecasubstituted porphyrins was synthesized through the optimization of the classic Suzuki–Miyaura coupling of peripheral haloaryl substituents with a range of boronic

• , borylation of a dodecasubstituted porphyrin’s meso-phenyl position was explored and a subsequent C–C coupling showed the polarity of the reaction can be reversed resulting in higher yields. X-ray analysis of the target compounds revealed the formation of supramolecular assemblies, capable of accommodating

• porphyrins Nonplanar porphyrins are known to form supramolecular assemblies [6], either through hydrogen-bonding networks or through π–π interactions. Examples of this can be seen in the trapping of Keggin-type heteropolyoxometalate (POM) through nonplanar Mo(V)–porphyrin complexes [58], or porphyrin

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

• sequential coordination of the water guests. The resulting supramolecular architecture, composed of CD and interconnected water molecules, is stabilized by hydrogen bonds between the water molecules and CDs. The pattern previously observed for α- and β-CD hydration is fully relevant for γ-CD: the hotspot of

Applications of microscopy and small angle scattering techniques for the characterisation of supramolecular gels

• Connor R. M. MacDonald and
• Emily R. Draper

Beilstein J. Org. Chem. 2024, 20, 2608–2634, doi:10.3762/bjoc.20.220

• supramolecular gels. Keywords: characterisation; electron microscopy; gelators; small angle scattering; supramolecular materials; Introduction Supramolecular gels are a versatile class of materials, and are of interest in many diverse applications from energy storage to cell culture [1][2]. The versatile

• gives rise to difficulties in understanding and predicting gel structure and properties [2]. In order to understand the supramolecular structure, a robust characterisation regime is required. A comprehensive work edited by Weiss and Térech discussed in detail the plethora of chemical systems

• , characterisation techniques, and applications of molecular gels; which still remains deeply insightful despite the rapid advancement of the field [10]. A more recent review by Yu et al. summarised a number of techniques used to characterise supramolecular materials [11]. Two of the most commonly used methods of

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

• been widely investigated in the past decades for application as fluorescent dyes [3][4][5], chirality inducers [6][7][8], acceptors for photoinduced electron transfer (PET) [9][10], and components of supramolecular assemblies [11][12][13][14]. Owing to the stable π-electronic systems showing unique

• . Moreover, the N-aryl-substituted TATA+ cations have been used as the building units of porous organic polymers for capturing CO2 [27]. Cations with characteristic electron-deficient planar triangular geometries were used as scaffolds for various supramolecular cage structures [28][29]. Although

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

• ], Szumna [37][38][39], Reinhoudt [40][41], Konishi [42][43][44], Tiefenbacher [45][46][47][48][49][50][51][52], Strongin [53][54][55] among others. The wide-ranging popularity of resorcin[n]arenes is rooted in the numerous applications these compounds have in supramolecular chemistry, e.g., catalysis and

• chloro species and flattened cone or boat for 1s [89]. Overall, access to electron-deficient and halogenated resorcin[4]arenes in one synthetic step provides building blocks to advance a wide range of chemical, physical, materials, and supramolecular applications. Future modifications of the protocol

• reported herein may impact the synthesis of other macrocyclic arene species, e.g., calix[n]arenes, calix[4]pyrroles, pillar[n]arenes, and cucurbit[n]urils [90][91][92]. Perspective Supramolecular chemistry is a mature field that has crossed boundaries into many other scientific areas. However, the work

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

• , this study should be of general interest in the understanding of weak interactions that are now important to so many areas of chemistry, such as crystal engineering and supramolecular chemistry. Synthesis of trihalogenated pyrans: a) Chiron approach to multivicinal inter-halide derived from

Synthesis, electrochemical properties, and antioxidant activity of sterically hindered catechols with 1,3,4-oxadiazole, 1,2,4-triazole, thiazole or pyridine fragments

• Daria A. Burmistrova,
• Andrey Galustyan,
• Nadezhda P. Pomortseva,
• Kristina D. Pashaeva,
• Maxim V. Arsenyev,
• Oleg P. Demidov,
• Mikhail A. Kiskin,
• Andrey I. Poddel’sky,
• Nadezhda T. Berberova and
• Ivan V. Smolyaninov

Beilstein J. Org. Chem. 2024, 20, 2378–2391, doi:10.3762/bjoc.20.202

• planes of the cycles corresponds to 5°). These pairs (Figure 3) are bound in a supramolecular chain along the 0c axis owing to two H-bonds between the OH group of catechol and the oxygen atom of nitro-group (O1–H1···O4B (1−x, 1−y, −1+z): the H1···O4 distance is 2.46(1) Å, the O1···O4 distance is 2.886(3

Novel truxene-based dipyrromethanes (DPMs): synthesis, spectroscopic characterization and photophysical properties

• Shakeel Alvi and
• Rashid Ali

Beilstein J. Org. Chem. 2024, 20, 2163–2170, doi:10.3762/bjoc.20.186

• ), organogels, molecular wires, self-assembly and so forth [14][15][16][17][18][19][20][21][22][23][24][25]. Moreover, nowadays these invaluable compounds have also received great attention of supramolecular chemists, and finds applications in sensing, catalysis, donor–acceptor systems, energy transfer and

• potential applications in the arena of supramolecular chemistry in general, sensing, molecular recognition and self-assembly in particular in has yet to be explored. Moreover, applications of the truxene derivatives in catalysis are also scared, and needs to be advanced in future research. Experimental

Multicomponent syntheses of pyrazoles via (3 + 2)-cyclocondensation and (3 + 2)-cycloaddition key steps

• Ignaz Betcke,
• Alissa C. Götzinger,
• Maryna M. Kornet and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2024, 20, 2024–2077, doi:10.3762/bjoc.20.178

• agrochemical uses of pyrazoles [13] include insecticides [14], herbicides [15], and fungicides [16]. Furthermore, they are widely applied for the assembly of supramolecular ensembles [17] and molecular systems capable of photoinduced electron transfer [18]. Due to their pertinent photophysical properties [19

Harnessing the versatility of hydrazones through electrosynthetic oxidative transformations

• Aurélie Claraz

Beilstein J. Org. Chem. 2024, 20, 1988–2004, doi:10.3762/bjoc.20.175

• ; Introduction Hydrazones represent an important class of organic compounds. They can be readily prepared through the condensation of hydrazine derivatives with aldehydes or ketones. They have found widespread applications in materials sciences and supramolecular chemistry [1][2][3][4][5]. Importantly, they are

2-Heteroarylethylamines in medicinal chemistry: a review of 2-phenethylamine satellite chemical space

• Carlos Nieto,
• Alejandro Manchado,
• Ángel García-González,
• David Díez and
• Narciso M. Garrido

Beilstein J. Org. Chem. 2024, 20, 1880–1893, doi:10.3762/bjoc.20.163

• activities of this supramolecular complex (Scheme 5), with positive in vitro activities in 20S proteasome core particles isolated from rabbit erythrocytes [28]. The sulfonamide 30 (Scheme 6) has been evaluated as inhibitor of human carbonic anhydrase I/II (hCA I and II), which catalyze the reversible

The Groebke–Blackburn–Bienaymé reaction in its maturity: innovation and improvements since its 21st birthday (2019–2023)

• Cristina Martini,
• Muhammad Idham Darussalam Mardjan and
• Andrea Basso

Beilstein J. Org. Chem. 2024, 20, 1839–1879, doi:10.3762/bjoc.20.162

• . Jung and Shinde, on the other hand, synthetized a supramolecular acid catalyst 14 combining β-cyclodextrins with succinic acid and tested it in a GBB reaction between isatin (15), indazol-3-amine (16) and pentyl isocyanide (17), yielding, after a ring expansion triggered by a retro-aza-ene reaction via

Synthesis and characterization of 1,2,3,4-naphthalene and anthracene diimides

• Adam D. Bass,
• Daniela Castellanos,
• Xavier A. Calicdan and
• Dennis D. Cao

Beilstein J. Org. Chem. 2024, 20, 1767–1772, doi:10.3762/bjoc.20.155

• robust polymers, supramolecular assemblies, and (opto)electronic materials. The vast majority of this research has focused on 1,2,4,5-benzene (pyromellitic), 1,4,5,8-naphthalene, and 3,4,9,10-perylene diimides. Beyond these, researchers have demonstrated that translocating the cyclic imides around the

• the π-interaction involving two 8-Ph molecules pointed in the same nominal direction is not linearly aligned, but is instead twisted by 19°. This angle, likely enforced by the sterics of the phenyl groups, may be an interesting approach to inducing helical turns in supramolecular assemblies derived

Supramolecular assemblies of amphiphilic donor–acceptor Stenhouse adducts as macroscopic soft scaffolds

• Ka-Lung Hung,
• Leong-Hung Cheung,
• Yikun Ren,
• Ming-Hin Chau,
• Yan-Yi Lam,
• Takashi Kajitani and
• Franco King-Chi Leung

Beilstein J. Org. Chem. 2024, 20, 1590–1603, doi:10.3762/bjoc.20.142

• Abstract In the design of photoharvesting and photoresponsive supramolecular systems in aqueous medium, the fabrication of amphiphilic photoswitches enables a noninvasive functional response through photoirradiation. Although most aqueous supramolecular assemblies are driven by high-energy and biodamaging

• moiety. The excellent photoswitchability in organic medium and the photoresponsiveness in aqueous medium, driven by visible light, were investigated by UV–vis absorption spectroscopy. The assembled supramolecular nanostructures were confirmed by electron microscopy, while the supramolecular packing was

• revealed by X-ray diffraction analysis. Upon visible-light irradiation, significant transformations of the DA geometry enabled transformations of the supramolecular assemblies on a microscopic scale, subsequently disassembling macroscopic soft scaffolds of DAs. The current work shows promising use for the

Selectfluor and alcohol-mediated synthesis of bicyclic oxyfluorination compounds by Wagner–Meerwein rearrangement

• Ziya Dağalan,
• Muhammed Hanifi Çelikoğlu,
• Saffet Çelik,
• Ramazan Koçak and
• Bilal Nişancı

Beilstein J. Org. Chem. 2024, 20, 1462–1467, doi:10.3762/bjoc.20.129

• materials, supramolecular and bioactive compounds [13][14][15][16][17]. To the best of our knowledge, although the oxyfluorination of various olefins with water and alcohols is known in the literature [18][19][20][21][22][23][24][25][26], there is no systematic study on the oxyfluorination of bicyclic