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

• medium or lead to the formation of the same final product as that achieved with formaldehyde, but through different reaction mechanisms. Due to the importance of this research, this review aims to summarize and analyze the significant efforts made in this regard in recent years. Major emphasis will be

• in MCR reactions applied to the synthesis of propargylamines and aminophosphonates. We will discuss the reaction conditions, mechanisms, and scope. Synthesis of propargylamines Propargylamines are essential building blocks for the synthesis of natural products or biologically active compounds in

Deep-blue emitting 9,10-bis(perfluorobenzyl)anthracene

• Long K. San,
• Sebastian Balser,
• Brian J. Reeves,
• Tyler T. Clikeman,
• Yu-Sheng Chen,
• Steven H. Strauss and
• Olga V. Boltalina

Beilstein J. Org. Chem. 2025, 21, 515–525, doi:10.3762/bjoc.21.39

• emitters for organic light emitting diodes (OLEDs) [4][5][6][7][8]. More recently, an increased interest in the studies of triplet–triplet annihilation mechanisms in anthracene emitter materials [9] and the design of efficient OLED emitters based on hyperfluorescence [10][11], which could exhibit high

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

• the synthesis of novel compounds and materials. While the mechanisms underlying mechanochemical reactions are still under investigation [47][48][49][50], the increasing body of research demonstrates the potential of this technique to revolutionize synthetic chemistry. Combining photochemistry with

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

• 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

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

• the fact that the fusing C–C bond between o-carborane and the pyrazole is not a double bond? Finally, in agreement with the above discussion on the bond lengths, Pierrefixe and Bickelhaupt revealed the underlying electronic bonding mechanisms in the π-electron and σ-electron systems that cause the

The effect of neighbouring group participation and possible long range remote group participation in O-glycosylation

• Rituparna Das and
• Balaram Mukhopadhyay

Beilstein J. Org. Chem. 2025, 21, 369–406, doi:10.3762/bjoc.21.27

• idea of glycosylation mechanisms to enable the readers to have a background idea as a reference before going to describe the role of protecting groups. The mechanistic pathway of glycosylation strongly depends on many factors, especially, the concentration of the participating moieties, the reaction

• ignored [26][27][28]. However, recent experimental, kinetic, and physical data reveal the incidence of more associative mechanisms [29][30][31] wherein the mechanistic pathway of glycosylation seems to lie at an interface of SN1–SN2 reaction (Scheme 1) [29]. The continuum mechanism expands in two

• pairs in glycosylation mechanisms was first reported by Rhind-Tutt and Vernon [44], and later reiterated by various authors, including the seminal graphical analysis of Lemieux and co-workers [45][46][47]. Thus, complete categorisation of the reaction in either of the subdomains of substitution reaction

Red light excitation: illuminating photocatalysis in a new spectrum

• Lucas Fortier,
• Corentin Lefebvre and
• Norbert Hoffmann

Beilstein J. Org. Chem. 2025, 21, 296–326, doi:10.3762/bjoc.21.22

• plausible mechanisms: a photoinduced electron transfer (PET) between the 3MLCT state of the copper complex and DCA or a triplet–triplet energy transfer (TTET) between the 3MLCT state of the copper complex and DCA. In both of these mechanisms, the involvement of a doublet excited-state of the radical anion

• can engage in electron-transfer mechanisms to enable radical cascade reactions under red-light irradiation (Scheme 9) [37]. These zinc(II)-based porphyrin catalysts operate via an oxidative quenching cycle, directly facilitating the transfer of an electron from the excited state of the porphyrin to

• hydrogen-atom-transfer mechanisms with a Hantzsch ester 34 as presented in Scheme 12. Moreover, the study has explored the impact of substrate steric hindrance and halogen bond strength on catalytic efficiency, revealing that bromo- and iodo-substrates react more efficiently, while chloro-substrates

Dioxazolones as electrophilic amide sources in copper-catalyzed and -mediated transformations

• Seungmin Lee,
• Minsuk Kim,
• Hyewon Han and
• Jongwoo Son

Beilstein J. Org. Chem. 2025, 21, 200–216, doi:10.3762/bjoc.21.12

• recent progress in the chemical transformation of dioxazolones using copper salts. This review provides an overview of the recent achievements in the use of copper salts as sustainable metal systems for the transformation of dioxazolones. This review also discusses several related proposed mechanisms

Recent advances in electrochemical copper catalysis for modern organic synthesis

• Yemin Kim and
• Won Jun Jang

Beilstein J. Org. Chem. 2025, 21, 155–178, doi:10.3762/bjoc.21.9

• , and benzamide, however, no relevant competitive oxidation peak was observed with only Cu(OAc)2. These results indicate that Cu(II) intermediate 5 was generated. Based on the mechanistic studies, the authors suggested plausible reaction mechanisms (Figure 4). First, the Cu(II) catalyst coordinates with

• -catalyzed electrochemical reactions are expected in the near future, developing powerful tools for sustainable and efficient organic syntheses. General mechanisms of traditional and radical-mediated cross-coupling reactions. Types of electrocatalysis (using anodic oxidation). Recent developments and

Nickel-catalyzed cross-coupling of 2-fluorobenzofurans with arylboronic acids via aromatic C–F bond activation

• Takeshi Fujita,
• Haruna Yabuki,
• Ryutaro Morioka,
• Kohei Fuchibe and
• Junji Ichikawa

Beilstein J. Org. Chem. 2025, 21, 146–154, doi:10.3762/bjoc.21.8

• mol %), and cod (10 mol %). bNi(cod)2 (20 mol %), PCy3 (40 mol %), and cod (20 mol %). cK3PO4 (1.2 equiv) was used as a base. dToluene–MeOH–H2O (5:1:1) was used as a solvent. Synthesis of 2-phenylbenzothiophene (5). Orthogonal approach to 2,5-diarylbenzofuran 3fa. Possible mechanisms. Formation of

Cu(OTf)₂-catalyzed multicomponent reactions

• Sara Colombo,
• Camilla Loro,
• Egle M. Beccalli,
• Gianluigi Broggini and
• Marta Papis

Beilstein J. Org. Chem. 2025, 21, 122–145, doi:10.3762/bjoc.21.7

• radical mechanisms. Synthesis of α-aminonitriles 1. Synthesis of β-amino ketone or β-amino ester derivatives 3. Synthesis of 1-(α-aminoalkyl)-2-naphthol derivatives 4. Synthesis of thioaminals 5. Synthesis of aryl- or amine-containing alkanes 6 and 7. Synthesis of 1-aryl-2-sulfonamidopropanes 8. Synthesis

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

• for the use in drug delivery systems [12]. In this regard, synthetic polypeptides emerge as a promising candidate for constructing biodegradable and biocompatible polymersomes. Leveraging the inherent presence of peptide-degrading mechanisms within the human body and the versatile chemical

Facile one-pot reduction of β-nitrostyrenes to phenethylamines using sodium borohydride and copper(II) chloride

• Laura D’Andrea and
• Simon Jademyr

Beilstein J. Org. Chem. 2025, 21, 39–46, doi:10.3762/bjoc.21.4

• Jackson mechanisms (product (a)), which, to date, were only associated to the catalytic hydrogenation of nitrobenzene analogues [35][36][37] (Figure 3). An attempt to identify the higher molecular masses observed by MS was made, and two intermediate structures are proposed in Figure 3. Together with (a

Ceratinadin G, a new psammaplysin derivative possessing a cyano group from a sponge of the genus Pseudoceratina

• Shin-ichiro Kurimoto,
• Kouta Inoue,
• Taito Ohno and
• Takaaki Kubota

Beilstein J. Org. Chem. 2024, 20, 3215–3220, doi:10.3762/bjoc.20.267

• [25][26][27][28]. It is known that natural nitrile compounds are biosynthesized through various mechanisms [29]. Rinehart and co-workers demonstrated that 2-(3,5-dibromo-4-hydroxyphenyl)acetonitrile is biosynthesized from ʟ-tyrosine via 3,5-dibromo-ʟ-tyrosine, based on experiments using 14C- and 15N

Discovery of ianthelliformisamines D–G from the sponge Suberea ianthelliformis and the total synthesis of ianthelliformisamine D

• Sasha Hayes,
• Yaoying Lu,
• Bernd H. A. Rehm and
• Rohan A. Davis

Beilstein J. Org. Chem. 2024, 20, 3205–3214, doi:10.3762/bjoc.20.266

• ; most of which are sessile and lack the ability to physically defend themselves from both predators and competitors and thus rely on chemical mechanisms for their defense [1]. Metabolites derived from marine sponges contribute more than half of all compounds identified from marine invertebrates [1][5

Direct trifluoroethylation of carbonyl sulfoxonium ylides using hypervalent iodine compounds

• Radell Echemendía,
• Carlee A. Montgomery,
• Fabio Cuzzucoli,
• Antonio C. B. Burtoloso and
• Graham K. Murphy

Beilstein J. Org. Chem. 2024, 20, 3182–3190, doi:10.3762/bjoc.20.263

• -mediated and SN2 reaction mechanisms. Ultimately, the nudged elastic band climbing image (NEB-CI) method predicted the SN2 pathway to be favoured, and transition state optimization showed this to possess a Gibbs free energy of activation of 24.3 kcal/mol. This report shows the ease with which sulfoxonium

• mesh) as a stationary phase (eluent n-hex/AcOEt 5:95%). Representative examples of fluorine containing, biologically active compounds. Possible mechanisms for the reaction of 1a and 2a leading to 3a (via B), proceeding via either halogen-bonded adducts and reductive elimination (path 1) or directly via

Hypervalent iodine-mediated intramolecular alkene halocyclisation

• Charu Bansal,
• Oliver Ruggles,
• Albert C. Rowett and
• Alastair J. J. Lennox

Beilstein J. Org. Chem. 2024, 20, 3113–3133, doi:10.3762/bjoc.20.258

• in poor yield with α preference for 7-membered rings 7 in a ratio of 1:9.3. The authors proposed two mechanisms for the reaction (Scheme 1). In pathway A (top), the alkene-activated iodonium is formed, intramolecular attack of nitrogen forms the 6-membered ring A before an SN2 reaction with the

• difluoroiodobenzene 10 is formed in situ, which is activated by HF. Two possible mechanisms were given for the synthesis of pyrrolidines 14, which are the same two proposed for the synthesis of piperidines 6 (Scheme 1). Either an alkene-activated iodonium is formed or an activated electrophilic nitrogen is generated

• tetrahydrofurans 25 and tetrahydropyrans 26. Unsaturated carboxylic acids 24 was also cyclised to form 5-membered fluorinated lactones 27. The mechanisms proposed for the cyclisation of unsaturated alcohols and carboxylic acids both proceed first through the activation of the alkene by the iodane (Scheme 11). The

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

• light turned out to be as effective as blue light, providing good yields of various photochemical reactions that proceed via both oxidative and reductive quenching mechanisms. Further, using of metal-free porphyrins as photocatalysts in bioorthogonal chemistry was explored. They can be utilized in

• evolution reaction (OER). There are several reviews focusing on the relationship between metallo-catalyst structures and HER, OER, and ORR performance/mechanisms, selection of the central metal ion, and peripheral functionalization of the catalysts [106][107][108][109]. This review summarizes recent

Enantioselective regiospecific addition of propargyltrichlorosilane to aldehydes catalyzed by biisoquinoline N,N’-dioxide

• Noble Brako,
• Sreerag Moorkkannur Narayanan,
• Amber Burns,
• Layla Auter,
• Valentino Cesiliano,
• Rajeev Prabhakar and
• Norito Takenaka

Beilstein J. Org. Chem. 2024, 20, 3069–3076, doi:10.3762/bjoc.20.255

• % yield with 61:39–92:8 enantiomeric ratios. Furthermore, possible mechanisms of propargyl–allenyl isomerization of propargyltrichlorosilane were computationally investigated. Keywords: α-allenic alcohol; computational chemistry; Lewis base catalysis; organocatalysis; propargyltrichlorosilane

• allenyltrichlorosilane in the presence of N,N-diisopropylethylamine upon standing after distillation (i.e., without solvent). Although the base-promoted propargyl–allenyl isomerization is well precedented in literature [60][61], we decided to investigate possible mechanisms of the propargyltrichlorosilane isomerization

• catalytic regiospecific addition reaction to aldehydes via a systematic catalyst structure–reactivity and selectivity relationship study, and computationally investigated possible mechanisms of N,N-diisopropylethylamine-promoted propargyl–allenyl isomerization of propargyltrichlorosilane. The observed

Chemical structure metagenomics of microbial natural products: surveying nonribosomal peptides and beyond

• Thomas Ma and
• John Chu

Beilstein J. Org. Chem. 2024, 20, 3050–3060, doi:10.3762/bjoc.20.253

• ingredient(s) and their mechanisms of action, humans have taken advantage of the therapeutic effects of herbal and microbial extracts for thousands of years [1]. We now know that natural products, genetically encoded secondary metabolites, are in most cases responsible for the desirable effects in these

Advances in radical peroxidation with hydroperoxides

• Oleg V. Bityukov,
• Pavel Yu. Serdyuchenko,
• Andrey S. Kirillov,
• Gennady I. Nikishin,
• Vera A. Vil’ and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2024, 20, 2959–3006, doi:10.3762/bjoc.20.249

• -exchanged Montmorillonite K10 [63] were presented (Scheme 19). Chemical and kinetic data confirm that the mechanisms of the described processes are probably of a radical nature with the formation of MOO-t-Bu complexes [61]. The proposed pathway of the peroxidation is shown on the example of 9-substituted

Structure and thermal stability of phosphorus-iodonium ylids

• Andrew Greener,
• Stephen P. Argent,
• Coby J. Clarke and
• Miriam L. O’Duill

Beilstein J. Org. Chem. 2024, 20, 2931–2939, doi:10.3762/bjoc.20.245

• ][26][27] and the mechanisms by which they decompose when heated through a systematic investigation of structural data from X-ray diffraction (XRD) and thermal stability data from differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The insights from this study will galvanise

Recent advances in transition-metal-free arylation reactions involving hypervalent iodine salts

• Ritu Mamgain,
• Kokila Sakthivel and
• Fateh V. Singh

Beilstein J. Org. Chem. 2024, 20, 2891–2920, doi:10.3762/bjoc.20.243

• five to seven-membered cyclic compounds [47]. Arylation reactions using diaryliodonium salts can occur through four distinct mechanisms. First, the arylation can occur under metal-free conditions, involving the formation of a three-membered ring transition state through ligand coupling, leading to the

Synthesis of tricarbonylated propargylamine and conversion to 2,5-disubstituted oxazole-4-carboxylates

• Kento Iwai,
• Akari Hikasa,
• Kotaro Yoshioka,
• Shinki Tani,
• Kazuto Umezu and
• Nagatoshi Nishiwaki

Beilstein J. Org. Chem. 2024, 20, 2827–2833, doi:10.3762/bjoc.20.238

• through successive nucleophilic additions to the central carbon atom of DEMO. Cyclization of 4a quenched by D2O. Plausible mechanisms for the ring closure of 4. Hydration of the ethynyl group of 4a. Optimization of the reaction conditions for the reaction of 1a with the lithium acetylide of 3a. Addition

Synthesis and antimycotic activity of new derivatives of imidazo[1,2-a]pyrimidines

• Dmitriy Yu. Vandyshev,
• Daria A. Mangusheva,
• Khidmet S. Shikhaliev,
• Kirill A. Scherbakov,
• Oleg N. Burov,
• Alexander D. Zagrebaev,
• Tatiana N. Khmelevskaya,
• Alexey S. Trenin and
• Fedor I. Zubkov

Beilstein J. Org. Chem. 2024, 20, 2806–2817, doi:10.3762/bjoc.20.236

• this work was a preliminary evaluation of the potential bioactivity of the obtained compounds. In particular, a molecular docking experiment to investigate the binding mechanisms to the CYP51 enzyme and an evaluation of the antifungal activity of imidazo[1,2-a]pyrimidines against Candida albicans were