Pd-catalyzed dehydrogenative arylation of arylhydrazines to access non-symmetric azobenzenes, including tetra-ortho derivatives

• Loris Geminiani,
• Kathrin Junge,
• Matthias Beller and
• Jean-François Soulé

Beilstein J. Org. Chem. 2025, 21, 2234–2242, doi:10.3762/bjoc.21.170

• product and side-products is presented in Figure 2B. The first reaction to be inhibited is the Pd-catalyzed denitrogenative cross-coupling, which leads to the formation of an array of biphenyl products [52][53][54]. This can be controlled by selecting appropriate catalysts and solvents. For instance, PdCl

Electrochemical cyclization of alkynes to construct five-membered nitrogen-heterocyclic rings

• Lifen Peng,
• Ting Wang,
• Zhiwen Yuan,
• Bin Li,
• Zilong Tang,
• Xirong Liu,
• Hui Li,
• Guofang Jiang,
• Chunling Zeng,
• Henry N. C. Wong and
• Xiao-Shui Peng

Beilstein J. Org. Chem. 2025, 21, 2173–2201, doi:10.3762/bjoc.21.166

• transformations far from thermodynamic equilibria have emerged abundantly with the consideration of green chemistry [89][90][91][92]. Redox-active organic compounds, transition metal coordinating compounds and even an electrode surface were commonly employed as catalysts in the electrochemical transformations [93

• anodic oxidation and AcO− capture. The hydrolysis of F then occurred to afford the final product 26a. This protocol featured with some advantages such as without any oxidants and metal catalysts, simple operation, good yields, high selectivity and wide substrate scope. Isoindolinone could be also

• reduction. The subsequent protonation of F occurred to complete the formation of 28. This approach, applying electrolyte as the proton sources, avoided the use of reductants and metal catalysts efficiently. In 2022, Guo developed an electrochemical intramolecular 1,2-amino oxygenation of alkyne to access

C2 to C6 biobased carbonyl platforms for fine chemistry

• Jingjing Jiang,
• Muhammad Noman Haider Tariq,
• Florence Popowycz,
• Yanlong Gu and
• Yves Queneau

Beilstein J. Org. Chem. 2025, 21, 2103–2172, doi:10.3762/bjoc.21.165

• diverse downstream products from biomass, with efforts for using clean and sustainable conditions in terms of solvents, reagents and catalysts. The topic of biomass conversion has been explored in multiple perspectives [23][24][25][26][27], and the purpose of the present review is to offer a specific

• for the synthesis of GA and GCA using activated carbon deposited Cu catalysts and different biomass-derived polyols as feedstock with exceptionally high atom utilization ≈93% and up to 90% yield (Scheme 1) [28]. Glycolaldehyde (GCA), the smallest sugar molecule, was used by Sels et al. for the

• -Hydroxypropanal (3-HPO) and 2,3-dihydroxypropanal (2,3-HPO) Xu et al. reported the cross-aldol reaction of formaldehyde and acetaldehyde for the synthesis of 3-hydroxypropanal and further reduction to 1,3-propanediol (PDO). The reaction was promoted by X-5Mg/SiO2 and Mg/SiO2 (X = Mn, Co, Ni, Fe) catalysts

The application of desymmetric enantioselective reduction of cyclic 1,3-dicarbonyl compounds in the total synthesis of terpenoid and alkaloid natural products

• Dong-Xing Tan and
• Fu-She Han

Beilstein J. Org. Chem. 2025, 21, 2085–2102, doi:10.3762/bjoc.21.164

• enantioselective reduction of some complex substrates, as well as suppressing the double reduction by-products and developing new types of catalysts. Moreover, the application of desymmetric enantioselective reduction of chain dicarbonyl compounds in natural products synthesis remains largely undeveloped although

Solar thermal fuels: azobenzene as a cyclic photon–heat transduction platform

• Jie Yan,
• Shaodong Sun,
• Minghao Wang and
• Si Wu

Beilstein J. Org. Chem. 2025, 21, 2036–2047, doi:10.3762/bjoc.21.159

• ) through structural or bond rearrangements, thereby enabling solar energy storage. This reversible process is termed "energy charging", while the subsequent transformation of high-energy photoisomers back to their ground state – triggered by external stimuli such as light, heat, or catalysts – releases

Switchable pathways of multicomponent heterocyclizations of 5-amino-1,2,4-triazoles with salicylaldehydes and pyruvic acid

• Yana I. Sakhno,
• Oleksander V. Buravov,
• Kostyantyn Yu. Yurkov,
• Anastasia Yu. Andryushchenko,
• Svitlana V. Shishkina and
• Valentyn A. Chebanov

Beilstein J. Org. Chem. 2025, 21, 2030–2035, doi:10.3762/bjoc.21.158

• -1,2,4-triazoles, is important because the formation of different chemotypes of final heterocyclic compounds are possible depending on the structure of the reagents, the solvents and the catalysts, and type of activation methods [7][8][9]. MCRs of aminotriazoles, methylene-active compounds, and

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

• important in pharmaceuticals, catalysts, and advanced materials due to their unique stereogenic scaffolds and associated properties. Consequently, synthetic chemists have been pursuing molecules featuring these forms of non-central chirality, where the stereogenic elements are not localized on a single

• parameterizing the relay of stereochemical information from the chiral catalysts to the prochiral substrates. In this study, we propose a stereocontrol connectivity index that quantitatively characterizes asymmetric reactions. The index could serve as a basis for classifying asymmetric reactions according to the

• positioning of stereochemically relevant elements, independent of the type of transformation. Additionally, the index enables the identification of the minimal set of structural features in a molecule that are recognized by chiral catalysts to achieve stereocontrol. Results and Discussion We envisaged that

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

• species are limited to aryl- [7][8][10] or heteroaryl groups [7][8]. In one example methyl ethers were used [9]. Under [Pd]-catalyzed conditions a syn-type addition is observed [8][11], while [Cu] catalysts promote anti-addition [7][10]. In substrates prone to cationic rearrangements (or hydride shifts

• , partial degradation of the starting material 7a was also observed. Among the tested solvents, EtOAc gave the best results (Table 1, entries 1–3, 7–18). As for reaction catalysts, Cu(I) salts demonstrated far better reactivity than Cu(II) salts, likely because the reaction proceeds via the Cu(I/III

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

• reactions, chemists have developed a series of catalysts composed of transition-metal cores and chiral ligands, which have been applied to various asymmetric reactions [50][51][52]. Compared to the enzymatic methods, the transition-metal-catalyzed approach may provide an advantage to access both enantiomers

• -catalyzed acylation Zn-based complexes are another class of effective catalysts used in desymmetrization of 1,3-diols, as reported by Trost and co-worker in 2003 [56]. In 2013, Trost et al. developed the synthesis of (−)-18-epi-peloruside A (Scheme 26) [68], and converted diol 204 into enantioenriched

• enantioselective desymmetrization of prochiral 1,3-diols within complex structures can be realized using organometallic catalysts composed of copper or zinc salts and different types of chiral ligands. In general, the ability to control the stereoselectivity of the product by using the enantiomer of the ligand in

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

• functional groups that might be incorporated into co-substrates [14]. The richness of potential connective chemistry, and the availability of alternative dirhodium catalysts with distinctive reactivity, was expected to expand the structural diversity of accessible reactive probes. Herein, we describe the

• with, we investigated reactions of the α-diazoamide substrates D1, D2 and D3 with the 16 co-substrates C1–16 catalysed by three diverse [21] dirhodium catalysts (Rh2piv4, Rh2pfb4 and Rh2cap4) i.e., an array of 144 reactions. An α-diazoamide substrate (20 μmol; 16 μL of a 1.25 M solution in CH2Cl2) and

• of each reaction was thus 200 μL, with final concentrations of 100 mM (for substrates), 500 mM (for co-substrates) and 1 mM (for catalysts). After 48 h, the outcome of the reactions was determined by analytical UPLC–MS with, additionally, evaporative light-scattering detection [22][23] to enable

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

• asymmetric Mannich reactions, the past two decades have witnessed the remarkable evolution of CPA catalysis into one of the most versatile platforms for achieving diverse enantioselective transformations [3][4][5][6][7][8]. CPA catalysts are generally recognized as bifunctional catalysts with two distinct

• catalytic sites. The OH group on the phosphorus atom functions as a Brønsted acid site, while P=O serves as a Lewis base site, which enables the simultaneous activation of both nucleophiles and electrophiles in one reaction (Figure 1). The chiral properties of the catalysts are derived from the chiral

• framework of the diol precursors, predominantly axially chiral structures such as BINOL, H8-BINOL, SPINOL and VAPOL scaffolds, which are widely used in the development of CPA catalysts. Furthermore, the ortho-aryl substitutions of the CPA catalyst can efficiently modulate the stereochemical and electronic

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

• enhance covalent and/or acid–base catalysis via any combination of non-covalent interactions (hydrogen bonding, π–π stacking, lipophilic interactions, etc) [4][5][6]. Inspired by enzymes, Nature's most efficient catalysts, chemists have long endeavored to synthesize catalytic materials in which multiple

• ][22]. These attributes allow us to construct MOF-based catalysts with active sites that are isolated within cavities of the same size range as small molecules and whose walls are decorated with precisely located functional groups. We can rationally elaborate these functional groups to modulate

• catalytic performance and/or systematically investigate the influence of a particular chemical or structural property on catalyst efficiency [23]. For examples of tailoring the pore environment in MOF-based catalysts to modulate catalytic performance, we can refer to the elegant work of Telfer and co

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

• 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

• [25]. However, these methods often require multiple synthetic steps and demanding conditions such as elevated temperatures, strong acidic or basic environments, and the use of expensive metal catalysts, which limit their broader applicability. To overcome these limitations, numerous catalytic

• cycloaddition, tandem annulation, intramolecular cyclization, and cross-coupling reactions are commonly employed under thermal conditions, utilizing metal catalysts based on Pd, Ru, Au, Cu, and Fe to access a wide array of substituted quinoline frameworks [29][30][31][32][33][34][35][36][37][38]. Conversely, in

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

Continuous-flow-enabled intensification in nitration processes: a review of technological developments and practical applications over the past decade

• Feng Zhou,
• Chuansong Duanmu,
• Yanxing Li,
• Jin Li,
• Haiqing Xu,
• Pan Wang and
• Kai Zhu

Beilstein J. Org. Chem. 2025, 21, 1678–1699, doi:10.3762/bjoc.21.132

• -flow nitration innovatively reimagines conventional methods for managing exothermic and selectivity-sensitive reactions, systematically analyzing four distinct approaches (nitration with mixed acids; nitration with fuming nitric acid; vapor-phase nitration; nitration with solid acid catalysts) to

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

• catalysis, particularly with palladium and silver, has proven to be highly effective, expanding the scope as well as the activation mode of chiral catalysts could greatly enrich reaction types and accessible structural diversity. Third, further investigation into the potential applications of the resulting

Photocatalysis and photochemistry in organic synthesis

• Timothy Noël and
• Bartholomäus Pieber

Beilstein J. Org. Chem. 2025, 21, 1645–1647, doi:10.3762/bjoc.21.128

• catalysis, and this arsenal of catalysts is constantly expanding. In this thematic issue, the Dell’Amico group describes the development of a new class of organic donor–acceptor photocatalysts that show promising activity for several transformations [18]. Additionally, Hoffmann and co-workers contributed a

Formal synthesis of a selective estrogen receptor modulator with tetrahydrofluorenone structure using [3 + 2 + 1] cycloaddition of yne-vinylcyclopropanes and CO

• Jing Zhang,
• Guanyu Zhang,
• Hongxi Bai and
• Zhi-Xiang Yu

Beilstein J. Org. Chem. 2025, 21, 1639–1644, doi:10.3762/bjoc.21.127

• introduce an ester group at the α position of the carbonyl group in 9 to get compound 10, which could have a more nucleophilic carbon better for the Heck reaction. 10 was obtained in 70% yield with a diastereomeric ratio of 4.5:1. Then, we screened various palladium catalysts and solvents to accomplish the

Transition-state aromaticity and its relationship with reactivity in pericyclic reactions

• Israel Fernández

Beilstein J. Org. Chem. 2025, 21, 1613–1626, doi:10.3762/bjoc.21.125

• ][46] (Figure 3a). Similar to the LA-catalyzed Diels–Alder reactions, the asynchronicity induced by the catalysts results in a reduced TS-aromaticity, which results from the reduction of the six-electron delocalization in the uncatalyzed reaction, as confirmed by the electron density of delocalized

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

• -methylindole 9a with 2a, carried out in the presence of Ni(hfacac)2 (50 mol %), unfortunately, did not give any identifiable products. Experiments with the catalysts presented in Table 1 were also unsuccessful. Nevertheless, favorable outcomes were achieved through a substantial decrease in catalyst loading

General method for the synthesis of enaminones via photocatalysis

• Paula Pérez-Ramos,
• Raquel G. Soengas and
• Humberto Rodríguez-Solla

Beilstein J. Org. Chem. 2025, 21, 1535–1543, doi:10.3762/bjoc.21.116

• the reactivity of unsaturated esters towards an aza-Michael addition is the use of transition metal complexes as catalysts/promoters [40][41][42]. Considering this background, we reasoned that Ni(II) could be a suitable catalyst for the amination of unsaturated systems. Initial investigations were

Calcium waste as a catalyst in the transesterification for demanding esters: scalability perspective

• Anton N. Potorochenko and
• Konstantin S. Rodygin

Beilstein J. Org. Chem. 2025, 21, 1520–1527, doi:10.3762/bjoc.21.114

• for esters requires the development of scalable production methods. Heterogeneous CaO-based catalysts for the production of esters by transesterification are promising catalytic systems for the production of these desired compounds. In this work, the application of calcium carbide slag, a byproduct of

• their manufacturing. The transesterification approach is an efficient way, which requires the use of a catalyst [44][45][46][47][48] and of course, there are many catalysts providing the desired transesterification products. However, the availability of the catalysts is limited, and the scope of

• industrially compatible catalysts is very narrow. The absence of an available large-tonnage catalyst is the principal limitation to the industrial production of commercially demanded esters. Calcium carbide slag, a waste product from acetylene production via hydrolysis of calcium carbide [49], was successfully

Photoredox-catalyzed arylation of isonitriles by diaryliodonium salts towards benzamides

• Nadezhda M. Metalnikova,
• Nikita S. Antonkin,
• Tuan K. Nguyen,
• Natalia S. Soldatova,
• Alexander V. Nyuchev,
• Mikhail A. Kinzhalov and
• Pavel S. Postnikov

Beilstein J. Org. Chem. 2025, 21, 1480–1488, doi:10.3762/bjoc.21.110

• of benzamides (Scheme 1A) [6]. Over the years, the basic reaction has been modified to imply various metal-containing catalysts [7][8][9][10][11][12][13][14][15][16][17][18], metal-free transformations that employ heteroarenes under harsh conditions [19], or using diazonium salts as arylating agents

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

• catalysts for direct C–H amination processes could be a significant breakthrough in optimising these reactions. Despite recent progress in site-selective C–H functionalisation [49], most reactions have remained reliant on homogeneous catalysis due to its molecularly defined nature. By contrast, the

• supported copper(II) catalysts on covalently modified silica [51][52], we have set out to develop a new heterogeneous catalyst with atomically distributed active sites for the mild and efficient C–H amination of benzoxazole. This approach was chosen because the silica derivatisation and copper deposition

• advantages of heterogeneous catalysis, but compared to other approaches, we aimed at eliminating the presence of bimetallic catalysts, the addition of a base [50], and the use of costly perfluorinated protic solvents [48]. In addition, this approach offers improved performance compared to photochemical C–H

Reactions of acryl thioamides with iminoiodinanes as a one-step synthesis of N-sulfonyl-2,3-dihydro-1,2-thiazoles

• Vladimir G. Ilkin,
• Pavel S. Silaichev,
• Valeriy O. Filimonov,
• Tetyana V. Beryozkina,
• Margarita D. Likhacheva,
• Pavel A. Slepukhin,
• Wim Dehaen and
• Vasiliy A. Bakulev

Beilstein J. Org. Chem. 2025, 21, 1397–1403, doi:10.3762/bjoc.21.104

• decrease in the yield of the target product to 78% over the same time (Table 1, entry 4). When the reaction was carried out in the absence of metal catalysts (Table 1, entries 5 and 6), the yields of the target product 3aa were generally lower (56–67%), and in some cases (Table 1, entries 8–11) the

• yields of 1,2-thiazoles 3aa–ae are slightly lower (70 vs 78%) than by method A. We also investigated the effect of chiral catalysts or ligands in the reaction of thioamide 1a with 2a; however, we were unable to achieve high enantiomeric purity of product 3aa (see Supporting Information File 1, Table S1

• iodonium salts. The search for optimal conditions for the process has been carried out. The optimized reaction found to proceed in the absence of metal catalysts, using 1.5 equiv of the iodonium salt at room temperature in DCM. Using the optimized procedure, a library of 31 novel 2,3-dihydro-1,2-thiazoles