α-Ketoglutaric acid in Ugi reactions and Ugi/aza-Wittig tandem reactions

• Vladyslav O. Honcharov,
• Yana I. Sakhno,
• Olena H. Shvets,
• Vyacheslav E. Saraev,
• Svitlana V. Shishkina,
• Tetyana V. Shcherbakova and
• Valentyn A. Chebanov

Beilstein J. Org. Chem. 2025, 21, 2021–2029, doi:10.3762/bjoc.21.157

• ; quinoxalinone derivative; Ugi reaction; Introduction Multicomponent reactions are powerful tools in organic chemistry that enable the synthesis of structurally complex and multifunctional compounds from three or more starting materials in a single synthetic step. They are widely used in drug discovery because

• , unlike conventional linear synthesis strategies, they enable the preparation of libraries of organic compounds in higher yields and with significantly less time, resources, and chemical waste [1][2][3][4][5]. The Ugi reaction, discovered in 1959 by Ivar Karl Ugi [6], is one of the classic multicomponent

• reactions, widely used as a green alternative for the synthesis of active pharmaceutical ingredients [7] and opens up the possibility of creating new compounds from the class of peptidomimetics [8][9][10], which often exhibit diverse biological effects [11] including antidiabetic [12], antiviral [13

Understanding the origin of stereoselectivity in the photochemical denitrogenation of 2,3-diazabicyclo[2.2.1]heptene and its derivatives with non-adiabatic molecular dynamics

• Leticia A. Gomes and
• Steven A. Lopez

Beilstein J. Org. Chem. 2025, 21, 2007–2020, doi:10.3762/bjoc.21.156

• producing energy-dense compounds [2][3]. One promising strategy to access strained compounds involves gas-evolution (e.g., CO or N2) because of the associated entropic driving force; this approach has had wide utility in photomedicine and organic synthesis. For example, photochemical decarboxylation has

• synthesis of strained compounds such as bicyclo[1.1.0]butane (BCB) and bicyclo[2.1.0]pentane (housane). The energy stored in strained σCC bonds of BCB and housane makes them important building blocks in the synthesis of complex molecular structures. BCBs have been employed in ring-opening reactions with

• nucleophiles [7][8][9][10][11], radicals [12][13][14][15] and electrophiles [16][17][18] to give cyclobutanes and cyclobutenes [19][20], which are building blocks in regio- and stereoselective synthesis [21][22][23][24][25][26][27] (Scheme 1a). Additionally, BCB has been used in bioconjugation due to its high

Measuring the stereogenic remoteness in non-central chirality: a stereocontrol connectivity index for asymmetric reactions

• Ivan Keng Wee On,
• Yu Kun Choo,
• Sambhav Baid and
• Ye Zhu

Beilstein J. Org. Chem. 2025, 21, 1995–2006, doi:10.3762/bjoc.21.155

• Ivan Keng Wee On Yu Kun Choo Sambhav Baid Ye Zhu Department of Chemistry, Faculty of Science, National University of Singapore, 3 Science Drive 2, Singapore 117543 10.3762/bjoc.21.155 Abstract Despite the rapid development of asymmetric synthesis, judging the remoteness of stereocontrol has

• chiral molecules. Keywords: asymmetric reactions; axial chirality; catalysis; planar chirality; stereocontrol; Introduction Chirality is a ubiquitous and fundamental phenomenon in nature and thus holds an irreplaceable position in organic synthesis. At its most rudimental definition, chirality in a

• among these scaffolds, the various types of chirality are permutations of substituents on diverse stereogenic elements (Scheme 1C). Although this analysis offers a unified view of chirality, the realization of these chiral systems through asymmetric synthesis is far from trivial. Stereogenic compounds

Aryl iodane-induced cascade arylation–1,2-silyl shift–heterocyclization of propargylsilanes under copper catalysis

• Rasma Kroņkalne,
• Rūdolfs Beļaunieks,
• Armands Sebris,
• Anatoly Mishnev and
• Māris Turks

Beilstein J. Org. Chem. 2025, 21, 1984–1994, doi:10.3762/bjoc.21.154

• Rasma Kronkalne Rudolfs Belaunieks Armands Sebris Anatoly Mishnev Maris Turks Institute of Chemistry and Chemical Technology, Faculty of Natural Sciences and Technology, Riga Technical University, P. Valdena str. 3, LV-1048, Riga, Latvia Latvian Institute of Organic Synthesis, Aizkraukles str. 21

• unidentified impurities. However, it turned out to be the key to achieving the best diene/indene ratio 10a/11a = 98:2. With the optimized conditions for aryldiene synthesis (Table 1, entries 16 and 17) we proceeded to explore the substrate scope (Table 2). Arylations employing aryl groups with electron

• in the context of 1,2-silyl shift and potential cyclization. Competing mechanistic pathways for diene 10 and indene 11 formation. Reaction scope for the synthesis of arylated tetrahydrofurans 8. Conditions: All reactions were performed on a 0.47 mmol scale. aStarting material 7d concentration: 0.1

Photochemical reduction of acylimidazolium salts

• Michael Jakob,
• Nick Bechler,
• Hassan Abdelwahab,
• Fabian Weber,
• Janos Wasternack,
• Leonardo Kleebauer,
• Jan P. Götze and
• Matthew N. Hopkinson

Beilstein J. Org. Chem. 2025, 21, 1973–1983, doi:10.3762/bjoc.21.153

• carboxylic acid derivatives involving hydrogen-atom transfer have not been reported despite the fundamental importance of carbonyl reduction processes in organic synthesis [46]. Here, we report the results of our investigation into such reactions using an acylazolium salt derived from benzoic acid as a model

• synthesis with complete reduction to the alcohol followed by partial re-oxidation often being conducted. Conclusion In conclusion, we have developed novel light-driven methodologies for the reduction of acylazolium salts using benzoylimidazolium triflate as a model substrate. In the presence of a

• . Given the importance of carboxyl reduction reactions in organic synthesis and the recent explosion in interest in light-mediated NHC-catalyzed coupling reactions, we believe this work will be of value to the community and further studies on these systems, including on the development of catalytic

Asymmetric total synthesis of tricyclic prostaglandin D2 metabolite methyl ester via oxidative radical cyclization

• Miao Xiao,
• Liuyang Pu,
• Qiaoli Shang,
• Lei Zhu and
• Jun Huang

Beilstein J. Org. Chem. 2025, 21, 1964–1972, doi:10.3762/bjoc.21.152

• available has prevented its practical use, and synthesis methods for tricyclic-PGDM methyl ester are required. Based on the utilization of oxidative radical cyclization for the stereoselective construction of the cyclopentanol subunit with three consecutive stereocenters, we describe an asymmetric total

• synthesis of tricyclic-PGDM methyl ester in 9 steps and 8% overall yield. Keywords: asymmetric total synthesis; oxidative radical cyclization; tricyclic prostaglandin D2 metabolite methyl ester; Introduction Prostaglandins (PGs), a family of hormone-like lipid compounds, are ubiquitous natural products

• effective tool in clinical applications [6]. However, the scarcity of metabolite 4 has prevented it from being used more widely, and thus synthesis methods for 4 are required. Compound 4 contains a cyclopentanol scaffold with stereogenicity at C8, C9, C11, and C12 (Scheme 1A). In addition, 4 is

Enantioselective desymmetrization strategy of prochiral 1,3-diols in natural product synthesis

• Lihua Wei,
• Rui Yang,
• Zhifeng Shi and
• Zhiqiang Ma

Beilstein J. Org. Chem. 2025, 21, 1932–1963, doi:10.3762/bjoc.21.151

• functionalization of one hydroxy group, offers beneficial procedures for accessing diverse structural motifs. In this review, we highlight a curated compilation of publications, focusing on the applications of enantioselective desymmetrization of prochiral 1,3-diols in the synthesis of natural products and

• biologically active molecules. Based on the reaction types, three strategies are discussed: enzymatic acylation, transition-metal-catalyzed acylation, and local desymmetrization. Keywords: asymmetric synthesis; desymmetrization; 1,3-diols; natural product; total synthesis; Introduction Natural products

• isolated from organisms are often asymmetric in their spatial structures, and these unique spatial structures are precisely what lead to their diverse biological activities [1][2][3][4]. For the synthesis of these natural products or bioactive molecules, chemists usually need to consider how to carry out

Rhodium-catalysed connective synthesis of diverse reactive probes bearing S(VI) electrophilic warheads

• Scott Rice,
• Julian Chesti,
• William R. T. Mosedale,
• Megan H. Wright,
• Stephen P. Marsden,
• Terry K. Smith and
• Adam Nelson

Beilstein J. Org. Chem. 2025, 21, 1924–1931, doi:10.3762/bjoc.21.150

• may be enabled by screening diverse sets of reactive probes. Most existing sets of reactive probes are armed with cysteine-directed warheads, a limitation that we sought to address. A connective synthesis was developed in which α-diazoamide substrates, armed with a S(VI) warhead, were reacted with

• . Remarkably, the synthetic approach was compatible with building blocks bearing three different S(VI) warheads, enabling the direct connective synthesis of diverse reactive probes armed with non-cysteine-directed warheads. Reactive probes that are synthetically accessible using our approach may be of value in

• the synthesis of structurally diverse reactive probes bearing S(VI) electrophiles. Proteome-wide screens have shown that S(VI) electrophiles predominantly target lysine and tyrosine [12], although other residues (e.g. serine) may also be targeted within enzyme active sites [13]. It was envisaged that

Synthesis of N-doped chiral macrocycles by regioselective palladium-catalyzed arylation

• Shuhai Qiu and
• Junzhi Liu

Beilstein J. Org. Chem. 2025, 21, 1917–1923, doi:10.3762/bjoc.21.149

• Shuhai Qiu Junzhi Liu Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, China State Key Laboratory of Synthetic Chemistry, HKU-CAS Joint Laboratory on New Materials and Shanghai-Hong Kong Joint Laboratory on Chemical Synthesis, The University of Hong Kong, Pokfulam

• chiral macrocycles, have been reported [17][25], highlighting a critical gap in the design of chiral macrocycles with tailored electronic landscapes. Herein, we reported the synthesis, characterizations and photophysical properties of inherent chiral N-doped macrocycles (Figure 1b) via regioselective

• demonstrated the synthesis and characterizations of N-doped macrocycles MC1–3 by palladium-catalyzed arylations. The molecular structures of the macrocyclic precursors and targets were unambiguously revealed by X-ray crystallographic characterization. These macrocycles exhibit strong fluorescence with ΦF

Synthesis, biological and electrochemical evaluation of glycidyl esters of phosphorus acids as potential anticancer drugs

• Almaz A. Zagidullin,
• Emil R. Bulatov,
• Mikhail N. Khrizanforov,
• Damir R. Davletshin,
• Elvina M. Gilyazova,
• Ivan A. Strelkov and
• Vasily A. Miluykov

Beilstein J. Org. Chem. 2025, 21, 1909–1916, doi:10.3762/bjoc.21.148

• . These findings provide important insights into the synthesis, cytotoxic activity, and biochemical reactivity of glycidyl esters of phosphorus acids, underscoring their potential as lead structures for further development in anticancer drug discovery and pharmaceutical research. Keywords: alkylating

• to a wide array of molecular targets [14][15][16]. The importance of phosphorus-containing drugs extends beyond their therapeutic applications; they also play a pivotal role in addressing specific medical conditions such as chronic kidney disease (CKD) [17][18]. The synthesis of organophosphorus

• encountered in the literature. In this paper, we report the synthesis, biological activity, and electrochemical evaluation of glycidyl esters of phosphorus acids. Results and Discussion Synthesis of glycidyl esters of phosphorus acids 1–3 Glycidyl esters of phosphorus acids 1–3 were obtained by condensation

Stereoselective electrochemical intramolecular imino-pinacol reaction: a straightforward entry to enantiopure piperazines

• Margherita Gazzotti,
• Fabrizio Medici,
• Valerio Chiroli,
• Laura Raimondi,
• Sergio Rossi and
• Maurizio Benaglia

Beilstein J. Org. Chem. 2025, 21, 1897–1908, doi:10.3762/bjoc.21.147

• diimines of aromatic aldehydes with trans-1,2-diaminocyclohexane for the synthesis of enantiopure tetrasubstituted piperazines has been investigated by an electrochemical approach. The methodology was successfully developed under both batch and continuous flow conditions, and afforded enantiomerically pure

• conditions, the continuous process afforded higher productivities and space-time yields than the batch reactions due to a short residence time. This work provides a mild, efficient, and scalable alternative to traditional methods for the synthesis of tetrasubstituted enantiopure piperazines, with potential

• products, agrochemicals, and pharmacologically active compounds. Enantiomerically pure 1,2-diamines and their derivatives are also increasingly used in stereoselective synthesis, particularly as chiral auxiliaries or as ligands for metal complexes in asymmetric catalysis [1]. Metal-based reductants

Preparation of spirocyclic oxindoles by cyclisation of an oxime to a nitrone and dipolar cycloaddition

• Beth L. Ritchie,
• Alexandra Longcake and
• Iain Coldham

Beilstein J. Org. Chem. 2025, 21, 1890–1896, doi:10.3762/bjoc.21.146

• -containing compounds makes use of intramolecular 1,3-dipolar cycloaddition reactions [15], including examples with nitrone ylides [16][17][18][19][20][21][22]. Our research group has exploited this approach for the synthesis of alkaloids such as myrioxazine A and aspidospermidine [23][24]. With a nitrone 1,3

• ) are quoted to the nearest 0.5 Hz with values in hertz (Hz). 13C NMR spectra were recorded on the above instrument at 100 MHz. Low- and high-resolution (accurate mass) mass spectra were recorded on a Walters LCT instrument using electrospray ionisation (ESI). Synthesis of the aldehyde 4 Sc(OTf)3 (0.63

Chiral phosphoric acid-catalyzed asymmetric synthesis of helically chiral, planarly chiral and inherently chiral molecules

• Wei Liu and
• Xiaoyu Yang

Beilstein J. Org. Chem. 2025, 21, 1864–1889, doi:10.3762/bjoc.21.145

• molecular chirality has been investigated comparatively less. This Review provides a comprehensive overview of the recent emerging advancements in asymmetric synthesis of planarly chiral, helically chiral and inherently chiral molecules using CPA catalysis, while offering insights into future developments

• pharmaceutical, agrochemical and asymmetric synthesis as well as materials science, to name a few examples. Molecular chirality is typically classified into four types of chiral elements: central (point) chirality, axial chirality, planar chirality and helical chirality (Figure 2). Moreover, unique forms of

• chirality originating from the rigid conformation of molecules lacking symmetry, which do not fit into the aforementioned four categories, are termed inherent chirality. Notable examples include inherently chiral calix[4]arenes and saddle-shaped medium-sized cyclic compounds. Catalytic asymmetric synthesis

Systematic pore lipophilization to enhance the efficiency of an amine-based MOF catalyst in the solvent-free Knoevenagel reaction

• Pricilla Matseketsa,
• Margret Kumbirayi Ruwimbo Pagare and
• Tendai Gadzikwa

Beilstein J. Org. Chem. 2025, 21, 1854–1863, doi:10.3762/bjoc.21.144

• efficiency. Keywords: metal-organic frameworks; post-synthesis modification; supramolecular catalysis; Introduction Most enzymatic reactions take place in multifunctional cavities in which multiple amino acid residues work cooperatively to orient and activate reactants [1][2][3]. These residues may also

• , the researchers tailored their catalyst via de novo solvothermal synthesis of their MOFs using differently substituted auxiliary linkers; a non-trivial effort which involves the synthesis of several new organic linkers and their subsequent assembly into completely new frameworks (Figure 1A). In this

• contrast to a previous reportthat observed an increase in the intermediate when a non-polar solvent is used in the grinding-assisted Knoevenagel reaction of the same reactants [56]. Conclusion By employing a covalent post synthesis modification strategy that selectively introduces lipophilic functionality

Photoswitches beyond azobenzene: a beginner’s guide

• Michela Marcon,
• Christoph Haag and
• Burkhard König

Beilstein J. Org. Chem. 2025, 21, 1808–1853, doi:10.3762/bjoc.21.143

• may be overwhelming: azobenzene is undoubtedly the most famous due to its easy synthesis and the extensively studied properties. However, there are several photoswitch classes beyond azobenzene with interesting properties that can be tailored to meet one’s needs. In this tutorial review, we aim to

• explain the important terminology and discuss the synthesis, switching mechanisms, and properties of seven interesting photoswitch classes, namely azoheteroarenes, diazocines, indigoid photoswitches, arylhydrazones, diarylethenes, fulgides, and spiropyrans. Keywords: photoswitches; photoswitch properties

• ; synthesis of photoswitches; switching mechanisms; tutorial review; Introduction Photophysical properties and switching mechanism Key learning points Switching mechanisms and the change in properties. Overview of the major classes of photoswitches beyond azobenzenes. Main synthetic pathways for their

Fe-catalyzed efficient synthesis of 2,4- and 4-substituted quinolines via C(sp²)–C(sp²) bond scission of styrenes

• Prafull A. Jagtap,
• Manish M. Petkar,
• Vaishnavi R. Sawant and
• Bhalchandra M. Bhanage

Beilstein J. Org. Chem. 2025, 21, 1799–1807, doi:10.3762/bjoc.21.142

• Prafull A. Jagtap Manish M. Petkar Vaishnavi R. Sawant Bhalchandra M. Bhanage Department of Chemistry, Institute of Chemical Technology, Mumbai-400019, India 10.3762/bjoc.21.142 Abstract Herein, we report a highly efficient, environmentally benign protocol for the domino synthesis of 2,4

• features of this protocol include the use of O2 as an ideal, green oxidant, operational simplicity and scalability, high atom- and step-economy, and cost-effectiveness, collectively enabling the single-step synthesis of two medicinally relevant N-heterocycles in excellent combined yields. Keywords: C–C

• probes for sensing and bioimaging applications (Figure 1) [16][17]. Quinoline-derived metal complexes have also demonstrated broad utility, functioning as effective catalysts in organic synthesis and finding applications across medicinal chemistry, materials science, photovoltaics, and chemical sensing

[3 + 2] Cycloaddition of thioformylium methylide with various arylidene-azolones in the synthesis of 7-thia-3-azaspiro[4.4]nonan-4-ones

• Daniil I. Rudik,
• Irina V. Tiushina,
• Anatoly I. Sokolov,
• Alexander Yu. Smirnov,
• Alexander R. Romanenko,
• Alexander A. Korlyukov,
• Andrey A. Mikhaylov and
• Mikhail S. Baranov

Beilstein J. Org. Chem. 2025, 21, 1791–1798, doi:10.3762/bjoc.21.141

• fluoride, is used for the synthesis of spirocyclic derivatives from arylidene-azolones. Four types of the corresponding heterocycles have been studied. A series of 7-thia-3-azaspiro[4.4]nonan-4-ones was obtained with yields varying from 17 to 99%. The stereochemical study revealed selective formation of

• (trimethylsilyl)methyl sulfide (compound I, Scheme 1) by the action of fluorides [21]. It reacts with a wide variety of compounds to form five-membered sulfur-containing heterocycles [22][23][24]. In particular, it can be used for the synthesis of 3,4-disubstituted tetrahydrothiophenes [25]. Partially substituted

• tetrahydrothiophenes are known to exhibit different biological activities [8]. However, to date the use of this reagent in the synthesis of spirocyclic derivatives to our knowledge is underinvestigated [26][27]. Results and Discussion In this work we present a systematic study of [3 + 2] cycloaddition of thioformylium

Synthesis of chiral cyclohexane-linked bisimidazolines

• Changmeng Xi,
• Qingshan Sun and
• Jiaxi Xu

Beilstein J. Org. Chem. 2025, 21, 1786–1790, doi:10.3762/bjoc.21.140

• vicinal amino alcohols as starting materials in their synthesis. However, it is difficult to tune the electronic effects of cHBOX ligands. Chiral cyclohexane-1,2-linked bisimidazolines possess similar structural features as cHBOX ligands and their electronic effect can be tuned by the introduction of

• different substituents on the NH moiety of the imidazoline ring. Herein, we designed and synthesized several sulfonylated cyclohexane-1,2-linked bisimidazoline (cHBim) ligands (Figure 1). Results and Discussion The synthesis of the chiral cyclohexane-linked bisimidazoline ligands started from enantiopure

• bisimidazoline ligands 5 on the stereocontrol in catalytic asymmetric reactions (Table 1). To improve the synthetic efficiency, a different strategy for the synthesis of a nonsulfonylated cyclohexane-linked bisimidazoline with subsequent sulfonylation with different sulfonyl chlorides was also considered and

Research progress on calixarene/pillararene-based controlled drug release systems

• Liu-Huan Yi,
• Jian Qin,
• Si-Ran Lu,
• Liu-Pan Yang,
• Li-Li Wang and
• Huan Yao

Beilstein J. Org. Chem. 2025, 21, 1757–1785, doi:10.3762/bjoc.21.139

• stimuli have garnered significant interest from researchers and have broad applications in the biomedical field. Aromatic macrocycles, including calixarenes and pillararenes, are considered ideal candidates for the construction of supramolecular drug delivery systems because of their simple synthesis

• , for example, classic macrocycles like cyclodextrins [38] and cucurbiturils [39]. In recent years, aromatic macrocycles such as calixarenes (CAs) [40] and pillararenes (PAs) [41] have attracted widespread attention from the industry and scientists due to their simple synthesis which only require a one

• -step synthesis, convenient modification that can be achieved by introducing functional groups, electron rich and hydrophobic cavities that can effectively recognize electron deficient or neutral guest molecules, and high selectivity in binding with the guest. Their applications are extensive in the

Unique halogen–π association detected in single crystals of C–N atropisomeric N-(2-halophenyl)quinolin-2-one derivatives and the thione analogue

• Mai Uchibori,
• Nanami Murate,
• Kanako Shima,
• Tatsunori Sakagami,
• Ko Kanehisa,
• Gary James Richards,
• Akiko Hori and
• Osamu Kitagawa

Beilstein J. Org. Chem. 2025, 21, 1748–1756, doi:10.3762/bjoc.21.138

• chemistry but also medicinal chemistry [10][11][12][13]. For example, 3-(2-bromophenyl)-2-methylquinazolin-4-one (I), which has a high rotational barrier about the N3–Ar bond, is known as mebroqualone possessing GABA agonist activity (Figure 1) [14][15]. Our group has been exploring asymmetric synthesis of

• C–N atropisomers and their structural properties for over 25 years [16][17]. As a part of the C–N atropisomeric chemistry, we succeeded in the asymmetric synthesis of mebroqualone (I) and the thione analogue II [18][19]. In the course of this study, it was found that intermolecular association in

• other C–N atropisomeric compounds. In this article, we report the synthesis of atropisomeric N-(2-halophenyl)quinolin-2-ones (1a: X = Br, 1b: X = Cl) and N-(2-bromophenyl)quinoline-2-thione (2a), and the analysis of halogen–mediated intermolecular interactions (halogen bonding and n–π* interaction

Thermodynamics and polarity-driven properties of fluorinated cyclopropanes

• Matheus P. Freitas

Beilstein J. Org. Chem. 2025, 21, 1742–1747, doi:10.3762/bjoc.21.137

• preclude its synthesis, as the all-cis-1,2,3-trifluorocyclopropane framework has been successfully prepared in earlier studies [17]. To better understand the intramolecular interactions that govern the stability of fluorinated cyclopropanes, the sets of di-, tri-, and tetrafluorinated cyclopropane isomers

Preparation of a furfural-derived enantioenriched vinyloxazoline building block and exploring its reactivity

• Madara Darzina,
• Anna Lielpetere and
• Aigars Jirgensons

Beilstein J. Org. Chem. 2025, 21, 1737–1741, doi:10.3762/bjoc.21.136

• Madara Darzina Anna Lielpetere Aigars Jirgensons Latvian Institute of Organic Synthesis Aizkraukles 21, Riga, LV-1006, Latvia Faculty of Natural Sciences and Technology, Riga Technical University, 3 P. Valdena Street, Riga LV-1048, Latvia 10.3762/bjoc.21.136 Abstract N-Alloc-protected furfuryl

• conditions compatible with the double bond and acetal functions. In this work, we present Torii-type electrosynthesis of ester 3d (PG = Alloc) and its transformation to the enantioenriched vinyloxazoline building block 6, which can be used for the asymmetric synthesis of complex molecules [19][20][21][22][23

• reaction, and we found that acetic acid served well for this purpose (Table 1, entry 4). Using the reaction conditions with acetic acid as additive, the reaction could be performed also in a 0.5 g scale for the synthesis of both ester enantiomers S-3d and R-3d (Table 1, entries 5 and 6). In the absence of

Convenient alternative synthesis of the Malassezia-derived virulence factor malassezione and related compounds

• Karu Ramesh and
• Stephen L. Bearne

Beilstein J. Org. Chem. 2025, 21, 1730–1736, doi:10.3762/bjoc.21.135

• ]. Unfortunately, testing of malassezione is limited by the lack of a convenient synthesis. Indeed, beyond isolating the compound from cultured M. furfur [11][20], the only reported synthetic route to malassezione is via an iron-catalyzed Fukuyama-type indole synthesis, which afforded the compound in low yield [18

• ]. Herein, we report an alternative synthesis from commercially available indole acetic acid, and demonstrate that the approach can be extended to related compounds. Results and Discussion Previously, malassezione had either been (i) isolated from cultures of M. furfur grown on ʟ-tryptophan as the sole

• subsequent iron-catalyzed reaction afforded 1 in only 35% yield. To avoid the low-yielding preparation of the isonitrile, we elected to use commercially available indole-3-acetic acid as the starting material, and to utilize an approach similar to that described for the synthesis of dibenzylketones from the

3,3'-Linked BINOL macrocycles: optimized synthesis of crown ethers featuring one or two BINOL units

• Somayyeh Kheirjou,
• Jan Riebe,
• Maike Thiele,
• Christoph Wölper and
• Jochen Niemeyer

Beilstein J. Org. Chem. 2025, 21, 1719–1729, doi:10.3762/bjoc.21.134

• highly efficient catalysts, chemosensors, and functional materials. We have recently made strides in developing macrocyclic organocatalysts; however, their synthesis remains challenging. In this work, we aimed to discover a straightforward method for producing a diverse range of chiral macrocycles

• , thereby enabling further exploration in the field of interlocked and macrocyclic organocatalysts. We successfully established optimized synthetic routes for the synthesis of chiral macrocycles containing one or two stereogenic units, featuring varying ring sizes and substituents (21 examples in total

• ]. For the synthesis of macrocycles M2 with two BINOL units, we relied on the monoiodide 12, which was first reacted in a two-fold Suzuki coupling to install the first linker, followed by silyl deprotection and introduction of the second linker via nucleophilic substitution [51]. Both procedures require

Approaches to stereoselective 1,1'-glycosylation

• Daniele Zucchetta and
• Alla Zamyatina

Beilstein J. Org. Chem. 2025, 21, 1700–1718, doi:10.3762/bjoc.21.133

• are involved. Consequently, approaches to 1,1′-glycosylation for the synthesis of nonreducing disaccharides with defined anomeric configurations are essential for the development of 1,1′-disaccharide-containing biomolecules used in vaccine research, as well as for therapeutic and diagnostic

• innovative, specialized approaches. While the synthesis of α,α-1,1'-linked nonreducing sugars was already comprehensively reviewed [36][37], the construction of β,β- and β,α-1,1'-glycosides has received noticeably less attention. This review provides an overview of the most recent developments in 1,1

• synthesis of symmetrically functionalized nonreducing disaccharide-based molecules. However, most biologically active molecules that contain nonreducing sugars are characterized by the presence of non-symmetrically distributed functional groups, which requires the use of selectively orthogonally protected