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

• substrate reactivity [64]. Cyclodextrins, cucurbiturils, cavitands, and calixarenes are representative [64][65][66][67][68][69][70], and typical features of these macrocycles are high symmetry and a hydrophobic cavity with polar edge groups. They tend to be synthesized as covalent cyclic oligomers in

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

• , it has been very insightful to study the molecular transformations associated with the generation of cationic species in conjugated aromatic oligomers displaying one-dimensional π-electron delocalization [1]. Oligothiophenes [2] and oligo(para-phenylene vinylenes) [3] have been used as models of

• antiaromatic character of 2 compared to 1. The decrease of the oxidation potentials with increasing antiaromaticity in the neutral states is opposite to the case of aromatic oligomers [21], where molecules with greater aromatic character have higher oxidation potentials. In addition, in 1•+ and 12+ the charge

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

Controlled oligomerization of [1.1.1]propellane through radical polarity matching: selective synthesis of SF₅- and CF₃SF₄-containing [2]staffanes

• Jón Atiba Buldt,
• Wang-Yeuk Kong,
• Yannick Kraemer,
• Masiel M. Belsuzarri,
• Ansh Hiten Patel,
• James C. Fettinger,
• Dean J. Tantillo and
• Cody Ross Pitts

Beilstein J. Org. Chem. 2024, 20, 3134–3143, doi:10.3762/bjoc.20.259

• -containing [2]staffane in the solid state. Keywords: pentafluorosulfanylation; [1.1.1]propellane; radical chain oligomerization; staffanes; strain-release; Introduction In various radical additions of X–Y across [1.1.1]propellane (1), functionalized oligomers known as [n]staffanes – with n > 1, where n

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

• manner, and from the few reports using 2-bromoresorcinol, it has been described to yield inseparable mixtures of oligomers [9][59]. Electron-withdrawing groups like carboxylic acids are another useful functional group instead of the halogen that provide a divergent route to other functional materials

Computational toolbox for the analysis of protein–glycan interactions

• Ferran Nieto-Fabregat,
• Maria Pia Lenza,
• Angela Marseglia,
• Cristina Di Carluccio,
• Antonio Molinaro,
• Alba Silipo and
• Roberta Marchetti

Beilstein J. Org. Chem. 2024, 20, 2084–2107, doi:10.3762/bjoc.20.180

• treated as flexible oligomers, allowing extensive conformational sampling of the glycoligand while maintaining glycosidic linkages within predetermined, energetically favorable minima to ensure biophysically realistic carbohydrate structures. GlycanDock handles the flexibility and complexity of glycans

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

• platinum cathode materials at 55 °C with a minimal amount of sodium methoxide, thereby limiting side products formation such as 133–135 or some oligomers of ethylenes (Scheme 28) [77]. In 2002, Okimoto et al. reported the indirect electrochemical oxidation of benzilhydrazones 138 using potassium iodide as

Introduction of peripheral nitrogen atoms to cyclo-meta-phenylenes

• Koki Ikemoto and
• Hiroyuki Isobe

Beilstein J. Org. Chem. 2024, 20, 1207–1212, doi:10.3762/bjoc.20.103

• . However, a MALDI-TOF MS analysis of the crude mixture showed that macrocyclisation did not complete to afford a complex mixture containing noncyclic, linear oligomers (Figure S1, Supporting Information File 1). After examining the Pd-catalysts, we found that macrocyclisation with PdCl2(dppf)·CH2Cl2 worked

Activity assays of NnlA homologs suggest the natural product N-nitroglycine is degraded by diverse bacteria

• Kara A. Strickland,
• Brenda Martinez Rodriguez,
• Ashley A. Holland,
• Shelby Wagner,
• Michelle Luna-Alva,
• David E. Graham and
• Jonathan D. Caranto

Beilstein J. Org. Chem. 2024, 20, 830–840, doi:10.3762/bjoc.20.75

• contaminants but are either undissociated higher oligomer states or are oligomers whose formation is induced by SDS treatment, which has been observed for other proteins [29][30]. To characterize these oligomer states of native protein, analytical size exclusion chromatography data were collected (Figure 2B

Switchable molecular tweezers: design and applications

• Pablo Msellem,
• Maksym Dekthiarenko,
• Nihal Hadj Seyd and
• Guillaume Vives

Beilstein J. Org. Chem. 2024, 20, 504–539, doi:10.3762/bjoc.20.45

Elucidating the glycan-binding specificity and structure of Cucumis melo agglutinin, a new R-type lectin

• Jon Lundstrøm,
• Emilie Gillon,
• Valérie Chazalet,
• Nicole Kerekes,
• Antonio Di Maio,
• Ten Feizi,
• Yan Liu,
• Annabelle Varrot and
• Daniel Bojar

Beilstein J. Org. Chem. 2024, 20, 306–320, doi:10.3762/bjoc.20.31

• , there are still significant gaps in our understanding. Further, in general, few melon lectins have been studied in detail. Some reports indicate the presence of chitooligosaccharide-binding (i.e., β1-4 GlcNAc oligomers) lectins from phloem exudates of melons [16][17], as well as R-type lectins in bitter

Anion–π catalysis on carbon allotropes

• M. Ángeles Gutiérrez López,
• Mei-Ling Tan,
• Giacomo Renno,
• Augustina Jozeliūnaitė,
• J. Jonathan Nué-Martinez,
• Javier Lopez-Andarias,
• Naomi Sakai and
• Stefan Matile

Beilstein J. Org. Chem. 2023, 19, 1881–1894, doi:10.3762/bjoc.19.140

• level. Compared to the sulfoxides in 46, the catalytic activity of dyad 47 decreased rather than increased despite stronger π acidity. Supported by computational predictions [80][81], record activities in anion–π catalysis with fullerene dimers called for higher oligomers. However, synthetic efforts

• were not fruitful, mostly due to poor solubility. Anion–π catalysis on carbon nanotubes With fullerenes confirmed as privileged scaffold for induced anion–π catalysis but higher oligomers inaccessible [12][67][80], the obvious next move was to switch to carbon nanotubes. Compared to the sixty free

Construction of hexabenzocoronene-based chiral nanographenes

• Ranran Li,
• Di Wang,
• Shengtao Li and
• Peng An

Beilstein J. Org. Chem. 2023, 19, 736–751, doi:10.3762/bjoc.19.54

• on representative examples of HBC-based chiral molecular NGs. All the examples in the context can be treated either as HBC-like monomers, or HBC-based dimers, trimers, tetramers, or oligomers. The synthesis of HBC is shown in Scheme 1. Pioneered by Scholl [30] and Clar [31] and further developed by

Synthesis, structure, and properties of switchable cross-conjugated 1,4-diaryl-1,3-butadiynes based on 1,8-bis(dimethylamino)naphthalene

• Semyon V. Tsybulin,
• Ekaterina A. Filatova,
• Alexander F. Pozharskii,
• Valery A. Ozeryanskii and
• Anna V. Gulevskaya

Beilstein J. Org. Chem. 2023, 19, 674–686, doi:10.3762/bjoc.19.49

• two 7-(arylethynyl)-1,8-bis(dimethylamino)naphthalene fragments was prepared via the Glaser–Hay oxidative dimerization of 2-ethynyl-7-(arylethynyl)-1,8-bis(dimethylamino)naphthalenes. The oligomers synthesized in this way are cross-conjugated systems, in which two conjugation pathways are possible: π

• the extent of π-conjugation and the efficiency of particular donor–acceptor conjugation path in these new compounds. X-ray structures and absorption spectra of doubly protonated tetrafluoroborate salts of the oligomers are also discussed. Keywords: 1,8-bis(dimethylamino)naphthalene; cross-conjugated

• systems; 1,4-diaryl-1,3-butadiynes; donor–acceptor systems; Glaser–Hay reaction; Introduction π-Conjugated oligomers and polymers attracted considerable attention from the very start as a promising class of semiconductors, chemosensors, and various electronic devices [1][2]. Although silicon and

Combretastatins D series and analogues: from isolation, synthetic challenges and biological activities

• Jorge de Lima Neto and
• Paulo Henrique Menezes

Beilstein J. Org. Chem. 2023, 19, 399–427, doi:10.3762/bjoc.19.31

• -OMe-corniculatolide A (5) in a 50% overall yield after 4 steps (Scheme 31) [69]. The authors did not isolate dimers or oligomers using this strategy and attributed this fact to the slow addition of the acyclic precursor 159 to a solution of Ph3P and DIAD (2.5 mM in PhMe). Using a similar strategy, the

Investigation of cationic ring-opening polymerization of 2-oxazolines in the “green” solvent dihydrolevoglucosenone

• Solomiia Borova and
• Robert Luxenhofer

Beilstein J. Org. Chem. 2023, 19, 217–230, doi:10.3762/bjoc.19.21

• for most POx, accordingly, it was used successfully only for the polymerization of EtOx [34]. Correia et al. used supercritical carbon dioxide for the synthesis of 2-oxazoline-based oligomers with antimicrobial properties and applied boron trifluoride etherate as the initiator [35]. However, carbamic

Preparation of β-cyclodextrin-based dimers with selectively methylated rims and their use for solubilization of tetracene

• Konstantin Lebedinskiy,
• Volodymyr Lobaz and
• Jindřich Jindřich

Beilstein J. Org. Chem. 2022, 18, 1596–1606, doi:10.3762/bjoc.18.170

• better effectiveness than other tested supramolecular hosts. Keywords: cyclodextrin; dimer; methylation; solubilization; tetracene; Introduction Cyclodextrins (CDs) are cyclic oligomers of glucose that play an important role in supramolecular chemistry [1]. The structure of any CD contains a

Oxa-Michael-initiated cascade reactions of levoglucosenone

• Julian Klepp,
• Thomas Bousfield,
• Hugh Cummins,
• Sarah V. A.-M. Legendre,
• Jason E. Camp and
• Ben W. Greatrex

Beilstein J. Org. Chem. 2022, 18, 1457–1462, doi:10.3762/bjoc.18.151

• processes in 1, such as the Baylis–Hillman reaction [14], and the Rauhut–Currier reaction which gives dimers such as 2 as well as higher oligomers [10][15]. An oxa-Michael-initiated three-component intermolecular reaction of 1 with furfural and water has been reported to result in enone 3 (Figure 1) [16

A Streptomyces P450 enzyme dimerizes isoflavones from plants

• Run-Zhou Liu,
• Shanchong Chen and
• Lihan Zhang

Beilstein J. Org. Chem. 2022, 18, 1107–1115, doi:10.3762/bjoc.18.113

• biocatalytic dimerization reactions [20]. Contrary to flavone dimers and oligomers being abundant in nature, only limited dimeric compounds have been reported for isoflavones. Isoflavones bear a characteristic 3-phenylchroman skeleton, which is formed by the B-ring migration from the flavonoid scaffold

First series of N-alkylamino peptoid homooligomers: solution phase synthesis and conformational investigation

• Maxime Pypec,
• Laurent Jouffret,
• Claude Taillefumier and
• Olivier Roy

Beilstein J. Org. Chem. 2022, 18, 845–854, doi:10.3762/bjoc.18.85

• Maxime Pypec Laurent Jouffret Claude Taillefumier Olivier Roy Université Clermont Auvergne, Clermont Auvergne INP, CNRS, ICCF, F-63000 Clermont–Ferrand, France 10.3762/bjoc.18.85 Abstract The synthesis and conformational analysis of the first series of peptoid oligomers composed of consecutive N

• chose to synthesize peptoid oligomers containing N-substituted methylamino amides, considering that the methods developed could be used for the synthesis of other members of this family (Figure 1B). Results and Discussion Synthesis A solution-phase approach using commercially available N-Boc-N

• to the Boc side chain protections. For the submonomer solution-phase synthesis of monomer 1 and oligomers 2–5, modifications from the standard synthesis conditions were required, notably for the substitution reaction. Thus, the first substitution reaction between benzyl bromoacetate and N-Boc-N

Heteroleptic metallosupramolecular aggregates/complexation for supramolecular catalysis

• Prodip Howlader and
• Michael Schmittel

Beilstein J. Org. Chem. 2022, 18, 597–630, doi:10.3762/bjoc.18.62

• hydrogen bonding. As a result, the Diels–Alder reaction of cyclopentadiene (128) and 127 was catalyzed. Upon addition of n-Bu4NCl, the open form was afforded that aggregated to oligomers [(126•Cl)n]n+ through intermolecular hydrogen bonding at the urea moieties. Now, activation of 127 stopped and catalysis

Polymer chemistry: fundamentals and applications

• Bernhard V. K. J. Schmidt

Beilstein J. Org. Chem. 2021, 17, 2922–2923, doi:10.3762/bjoc.17.200

• , where oligomers bring molecular precision from organic chemistry together with materials properties from polymer chemistry [5]. Especially in the challenge of transformation to a more sustainable polymer science, organic chemistry can give significant support in the development of greener polymer

Iron-catalyzed domino coupling reactions of π-systems

• Austin Pounder and
• William Tam

Beilstein J. Org. Chem. 2021, 17, 2848–2893, doi:10.3762/bjoc.17.196

• a four-component radical dual difunctionalization and ordered assembly of two chemically distinct alkenes 114/115, aldehyde 65, and tert-butyl peroxide (Scheme 23) [108]. In order to selectively couple one alkene to another, without the formation of oligomers, the authors utilized the different

Adjusting the length of supramolecular polymer bottlebrushes by top-down approaches

• Tobias Klein,
• Franka V. Gruschwitz,
• Maren T. Kuchenbrod,
• Ivo Nischang,
• Stephanie Hoeppener and
• Johannes C. Brendel

Beilstein J. Org. Chem. 2021, 17, 2621–2628, doi:10.3762/bjoc.17.175

• min of centrifugation, no further change could be observed since the peak at this low elution time already corresponded to very small oligomers (Figure 3A). For BTP, a stronger downward shift of the peak maximum from 70 to 45 min could be observed after 1 min of mixing. Similar to BTU, the increase in

Progress and challenges in the synthesis of sequence controlled polysaccharides

• Giulio Fittolani,
• Theodore Tyrikos-Ergas,
• Denisa Vargová,
• Manishkumar A. Chaube and
• Martina Delbianco

Beilstein J. Org. Chem. 2021, 17, 1981–2025, doi:10.3762/bjoc.17.129

• polysaccharides longer than hexasaccharides. Shorter oligomers are discussed when they represent a key step towards the synthesis of the corresponding polysaccharide. Polymers based on a sugar backbone connected via glycosidic linkages are analyzed, excluding glycopolymers and other mimetics. Extraction

• better understanding of cellulose’s properties are hindered by its poor solubility in most solvents. Relatively short oligomers with DPs of 6–10 tend to aggregate and precipitate out of solution [54], making isolation of pure samples troublesome. Much effort has been put to tune the synthetic conditions

• developments of synthetic cellulose until the year 2005 were discussed in a previous review [58], therefore we will focus only on recent reports. A detailed discussion on the synthesis of cellulose oligomers by enzymatic depolymerization [59] and phosphorylase [60] can be found elsewhere. The first successful