Harnessing tethered nitreniums for diastereoselective amino-sulfonoxylation of alkenes

• Shyam Sathyamoorthi,
• Appasaheb K. Nirpal,
• Dnyaneshwar A. Gorve and
• Steven P. Kelley

Beilstein J. Org. Chem. 2025, 21, 947–954, doi:10.3762/bjoc.21.78

• equivalent of commercial iodomesitylene diacetate (CAS [33035-41-5]) and 1 equivalent of MsOH (Table 1, entry 4). Here, it was necessary to maintain a temperature of 0 °C, as vigorous bubbling and rapid decomposition occurred when the reaction was initiated at room temperature. In all cases (Table 1), only a

• delivering product (Table 2, entries 1 and 3–5). With our standard conditions of stirring substrate with 1.5 equivalents of PhI(OH)(OTs) in CH2Cl2 at room temperature, the yield of product markedly suffered with N-isopropoxy carbamate substrate 3 (Table 2, entry 2). Here, we hypothesize that the increased

Study of tribenzo[b,d,f]azepine as donor in D–A photocatalysts

• Katy Medrano-Uribe,
• Jorge Humbrías-Martín and
• Luca Dell’Amico

Beilstein J. Org. Chem. 2025, 21, 935–944, doi:10.3762/bjoc.21.76

• , with values of 16%, 14%, and 14%, respectively. The lowest values were obtained for molecules 5a and 5b (7% and 6%, each). Remarkably, compound 5e demonstrated minimal luminescence in nearly all solvents at room temperature. This behavior has been previously reported and is believed to be due to strong

Silver(I) triflate-catalyzed post-Ugi synthesis of pyrazolodiazepines

• Muhammad Hasan,
• Anatoly A. Peshkov,
• Syed Anis Ali Shah,
• Andrey Belyaev,
• Chang-Keun Lim,
• Shunyi Wang and
• Vsevolod A. Peshkov

Beilstein J. Org. Chem. 2025, 21, 915–925, doi:10.3762/bjoc.21.74

• , when performed at room temperature, proceeded with lower efficiency compared to the reaction at 70 °C, leaving some of the starting 1H-pyrazole-3-carbaldehyde (14a) unreacted. Propargylamide 15a was selected as a model substrate to optimize the reaction conditions for the intramolecular

• pyrazole-tethered propargylamides 15 via U4CR. Conditions: Unless otherwise specified, the reactions were run on a 1.0 mmol scale in methanol (5 mL). The reactions were conducted in screw cap vials at 70 °C for 24 hours and isolated yields are reported. aConducted on a 6.0 mmol scale. bConducted at room

• temperature. cConducted on a 2.0 mmol scale. dConducted on a 1.5 mmol scale. Scope of the silver(I) triflate-catalyzed synthesis of pyrazolo[1,5-a][1,4]diazepines. Conditions: Unless otherwise specified, the reactions were run on 0.2 mmol scale using 20 mol % of AgOTf in dioxane (1 mL). The reactions were

Recent advances in controllable/divergent synthesis

• Jilei Cao,
• Leiyang Bai and
• Xuefeng Jiang

Beilstein J. Org. Chem. 2025, 21, 890–914, doi:10.3762/bjoc.21.73

• (cod)Cl]2 and the Carreira chiral phosphoramidite ligand (S)-L10, along with the addition of 3,5-dichlorobenzoic acid as an additive in MeOH at room temperature, the reaction proceeded smoothly for 10 hours to yield the aminated product 51. Interestingly, when the reaction was quenched after 6 minutes

• and n-BuLi, followed by a reaction with ZnCl2 at room temperature. The product is then hydrolyzed with a NaOH solution of H2O2 to yield amino alcohols. The mechanism involves the formation of borate intermediate Int-79 from substrate 83 under the action of CH2BrLi. This is followed by an N-1,2

Regioselective formal hydrocyanation of allenes: synthesis of β,γ-unsaturated nitriles with α-all-carbon quaternary centers

• Seeun Lim,
• Teresa Kim and
• Yunmi Lee

Beilstein J. Org. Chem. 2025, 21, 800–806, doi:10.3762/bjoc.21.63

• , the hydride addition of DIBAL-H to allene 1a catalyzed by 5 mol % IPrCuCl as the optimal catalyst selectively generated the allylaluminum intermediate 2a with >98% conversion [30]. Subsequent addition of one equivalent of TsCN to 2a in a single vessel at room temperature proceeded regioselectively

• scope for the formal hydrocyanation with 1,1-disubstituted and 1,1,3-trisubstituted allenes was examined (Scheme 3). All reactions were performed in the presence of 5 mol % IPrCuCl to generate the allylaluminum reagents in situ, followed by cyanation at room temperature for 30 min. This method

Recent advances in the electrochemical synthesis of organophosphorus compounds

• Babak Kaboudin,
• Milad Behroozi,
• Sepideh Sadighi and
• Fatemeh Asgharzadeh

Beilstein J. Org. Chem. 2025, 21, 770–797, doi:10.3762/bjoc.21.61

• undivided cell at room temperature, and three different electrodes, graphite, platinum, and glassy carbon (GC), were examined during the reaction. The best result was obtained when platinum electrodes were used as the anode and cathode. Although the reaction was less efficient in undivided cells, increasing

• electrochemical method. They have synthesized 30 different thiazole phosphine oxides with up to 91% yield at room temperature without using an external metal or oxidant. The reaction was carried out in an undivided cell using glassy carbon as the anode and foamed copper as the cathode electrodes at a constant

• et al. [59] reported an electrochemical method for the synthesis of phosphorylation of oxindoles and indolo[2,1-a]isoquinoline-6(5H)-ones using Cp2Fe through a radical addition/cyclization reaction at room temperature under argon gas. This research shows that this method is effective with various

Development and mechanistic studies of calcium–BINOL phosphate-catalyzed hydrocyanation of hydrazones

• Carola Tortora,
• Christian A. Fischer,
• Sascha Kohlbauer,
• Alexandru Zamfir,
• Gerd M. Ballmann,
• Jürgen Pahl,
• Sjoerd Harder and
• Svetlana B. Tsogoeva

Beilstein J. Org. Chem. 2025, 21, 755–765, doi:10.3762/bjoc.21.59

• BINOL phosphate/Ca(OiPr)2. In the presence of two equivalents of TMSCN, complex 4 gave a quantitative conversion to the product 2, whereby the phosphoric acid BIPO4-H ligand 3 did not catalyze this hydrocyanation. At room temperature, a nearly full conversion can already be achieved within 2–12 hours

Copper-catalyzed domino cyclization of anilines and cyclobutanone oxime: a scalable and versatile route to spirotetrahydroquinoline derivatives

• Qingqing Jiang,
• Xinyi Lei,
• Pan Gao and
• Yu Yuan

Beilstein J. Org. Chem. 2025, 21, 749–754, doi:10.3762/bjoc.21.58

• moderate yield (Table 1, entry 6). Conducting the reaction at room temperature (rt) instead of the optimal elevated temperature resulted in a lower yield (Table 1, entry 7). Increasing the reaction temperature to 100 °C did not improve the yield (Table 1, entry 8). Having established the optimal reaction

Synthesis of HBC fluorophores with an electrophilic handle for covalent attachment to Pepper RNA

• Raphael Bereiter and
• Ronald Micura

Beilstein J. Org. Chem. 2025, 21, 727–735, doi:10.3762/bjoc.21.56

• obtained in general procedure B was dissolved in dichloromethane and cooled to 0 °C under argon atmosphere. Then, triphenylphosphine and carbon tetrabromide were added and stirred at room temperature for two hours. Afterwards, the entire mixture was loaded on a silica gel column and eluted with 100

• % dichloromethane. General procedure D. In a manner similar to [11], the product obtained in general procedure B, methanesulfonyl chloride, and triethylamine were dissolved in dichloromethane and stirred overnight at room temperature. After reaction control and 100% consumption of the starting material, the entire

Acyclic cucurbit[n]uril bearing alkyl sulfate ionic groups

• Christian Akakpo,
• Peter Y. Zavalij and
• Lyle Isaacs

Beilstein J. Org. Chem. 2025, 21, 717–726, doi:10.3762/bjoc.21.55

• shows an ion at m/z = 751.13 which corresponds to [C1 − 2Na]2−. Inherent aqueous solubility of C1 After having firmly established the structure of C1 we decided to determine its inherent aqueous solubility. For this purpose, we added an excess of solid C1 to D2O and stirred the solution at room

• temperature overnight. Afterwards, the mixture was centrifuged (4400 rpm, 10 min) to pellet excess insoluble C1. An aliquot of the supernatant and a solution of dimethyl malonic acid as a non-binding internal standard of known concentration were transferred to an NMR tube followed by collection of a 1H NMR

Asymmetric synthesis of fluorinated derivatives of aromatic and γ-branched amino acids via a chiral Ni(II) complex

• Maurizio Iannuzzi,
• Thomas Hohmann,
• Michael Dyrks,
• Kilian Haoues,
• Katarzyna Salamon-Krokosz and
• Beate Koksch

Beilstein J. Org. Chem. 2025, 21, 659–669, doi:10.3762/bjoc.21.52

• identified as optimal delivering a yield of alkylated complex of 60% (Table 1, entry 4). With DBU as base different solvents differing in polarity have been tested. At room temperature, acetonitrile proved best and increased the yield to 88% (Table 1, entry 11). Lowering the temperature to 0 °C led to a

• (II) complex of bisTfMePhe have differed significantly. Here, sodium hydride (NaH) was identified as optimal base leading to a yield of 85% when using DMF as solvent at 0 °C to room temperature (Table 2, entry 4). Testing different base equivalents, solvents, solvent mixtures and temperatures didn’t

• lead to any yield improvement (Table 2, entries 7–13). Herein, using dimethylformamide (DMF), different equiv of alkyl bromide were further screened resulting in a yield of 93%. Thus, 1.5 equiv NaH with 1.5 equiv alkyl bromide in DMF at 0 °C to room temperature have been identified as optimal

Recent advances in allylation of chiral secondary alkylcopper species

• Minjae Kim,
• Gwanggyun Kim,
• Doyoon Kim,
• Jun Hee Lee and
• Seung Hwan Cho

Beilstein J. Org. Chem. 2025, 21, 639–658, doi:10.3762/bjoc.21.51

• optimization revealed LiOt-Bu and diphenyl phosphate as the optimal metal alkoxide and leaving group, delivering the desired product 32 in high yield and high enantioselectivity at room temperature with only 2 mol % catalyst loading. The scope of this transformation proved to be remarkably broad. In addition

Entry to 2-aminoprolines via electrochemical decarboxylative amidation of N‑acetylamino malonic acid monoesters

• Olesja Koleda,
• Janis Sadauskis,
• Darja Antonenko,
• Edvards Janis Treijs,
• Raivis Davis Steberis and
• Edgars Suna

Beilstein J. Org. Chem. 2025, 21, 630–638, doi:10.3762/bjoc.21.50

• conditions at room temperature, and 2.0 F charge (if not otherwise noticed) with current density of 12 mA/cm2 was passed through the colorless reaction solution. The resulting clear, colorless (sometimes pale yellow) solution was concentrated under reduced pressure and the crude product was purified by

Photocatalyzed elaboration of antibody-based bioconjugates

• Marine Le Stum,
• Eugénie Romero and
• Gary A. Molander

Beilstein J. Org. Chem. 2025, 21, 616–629, doi:10.3762/bjoc.21.49

• for the types of reactions that can be used for the elaboration of ADCs. Among the signature features of photochemical, single-electron transformations is their ability to be conducted in dilute aqueous media at room temperature and at neutral pH [47]. Additionally, the distinctive mechanistic

Semisynthetic derivatives of massarilactone D with cytotoxic and nematicidal activities

• Rémy B. Teponno,
• Sara R. Noumeur and
• Marc Stadler

Beilstein J. Org. Chem. 2025, 21, 607–615, doi:10.3762/bjoc.21.48

• ), solvent A: H2O + 0.1% formic acid; solvent B: acetonitrile (ACN) + 0.1% formic acid, gradient: 5% B for 0.5 min, increasing to 100% B in 20 min, maintaining isocratic conditions at 100% B for 10 min, flow = 0.6 mL/min, UV–vis detection 190–600 nm]. Preparative HPLC was achieved at room temperature on an

• mixture was stirred at room temperature overnight. The reaction mixture was suspended in water (25 mL) and extracted with CH2Cl2 (2 × 25 mL). The combined organic layer was evaporated to dryness to give a residue, which was dissolved in methanol (300 μL) and purified by preparative HPLC [ChemStation

• , 0.062 mmol) was dissolved in CH2Cl2 (10 mL). Triethylamine (20 μL) and cinnamoyl chloride (50 mg, 0.30 mmol) were added to the solution. After adding a catalytic amount of 4-dimethylaminopyridine, the reaction mixture was stirred at room temperature overnight. The reaction mixture was suspended in water

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

• occurred at room temperature. The mild reaction conditions for both strategies (“free” or immobilized glyoxylic acid) allows for a broad scope in terms of 2-aminoazines and isocyanide components (some examples are shown in Scheme 34). It is important to note that these imidazo heterocycles have been

Vinylogous functionalization of 4-alkylidene-5-aminopyrazoles with methyl trifluoropyruvates

• Judit Hostalet-Romero,
• Laura Carceller-Ferrer,
• Gonzalo Blay,
• Amparo Sanz-Marco,
• José R. Pedro and
• Carlos Vila

Beilstein J. Org. Chem. 2025, 21, 533–540, doi:10.3762/bjoc.21.41

• (Table 1). First, we tried several solvents (dichloromethane, toluene and dichloroethane, entries 1–3 in Table 1) at room temperature, obtaining product 5aaa in yields around 50% with high diastereoselectivity (up to 6:1) after several days. Increasing the temperature to 50 °C (Table 1, entries 4 and 5

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

• Abstract A new deep-blue emitting and highly fluorescent anthracene (ANTH) derivative containing perfluorobenzyl (BnF) groups, 9,10-ANTH(BnF)2, was synthesized in a single step reaction of ANTH or ANTH(Br)2 with BnFI, using either a high-temperature Cu-/Na2S2O3-promoted reaction or via a room-temperature

• were shown to form from ANTH(RF)n derivatives within minutes at room temperature in the presence of oxygen when irradiated with a high pressure mercury lamp [32]. When 9,10-bis(perfluorooctyl)anthracene was dissolved in CHCl3 and irradiated for 350 minutes, photodecomposition was observed. However, the

• . The new compounds 9-ANTH(BnF) and 9,10-ANTH(BnF)2 were prepared in varying amounts using several synthetic procedures, including conventional high-temperature Cu-/Na2S2O3-promoted reactions and a room-temperature photochemical reaction. The former approach resulted in challenging work-ups, low yields

Unprecedented visible light-initiated topochemical [2 + 2] cycloaddition in a functionalized bimane dye

• Metodej Dvoracek,
• Brendan Twamley,
• Mathias O. Senge and
• Mikhail A. Filatov

Beilstein J. Org. Chem. 2025, 21, 500–509, doi:10.3762/bjoc.21.37

• included two additional bimane samples, Me2B and Me4B. These samples were crystallized from a MeOH–DCM 1:1 (v/v) mixture which was left to slowly evaporate over the course of several days at room temperature, followed by single-crystal X-ray diffraction to determine their structure (Figure 4) and crystal

• )bimane (DMOCDO10) and syn-(Me,Me)bimane (DXABIM10) [26], a room temperature structure of Me4B (TNZBCO10) [27], and a planar syn-(H,ethynyl)bimane (WAYHEJ) [28]. Optical properties The optical properties of the three bimanes were measured to investigate differences in their excited state properties, as

• 1:1 (v/v) solution which was left to evaporate at room temperature over the course of a few days. Photophysical properties Fluorescence spectra were measured on a Horiba FluoroMax Plus spectrofluorimeter. UV–vis spectra were measured on a Shimadzu UV-1900i UV–vis spectrophotometer. Absorption and

Synthesis of electrophile-tethered preQ₁ analogs for covalent attachment to preQ₁ RNA

• Laurin Flemmich and
• Ronald Micura

Beilstein J. Org. Chem. 2025, 21, 483–489, doi:10.3762/bjoc.21.35

• methanol (1.3 mL). Anhydrous magnesium sulfate (340 mg, 2.82 mmol, 10 equiv) and the respective amino alcohol (2.82 mmol, 10 equiv) were added. The mixture was sonicated for 30 minutes and subsequently stirred at room temperature for 16 h. After cooling to 0 °C, sodium borohydride (96.1 mg, 2.54 mmol, 9

• equiv) was added in portions over the course of 1 h. The mixture was stirred for additional 2.5 h at room temperature. Afterwards, the volatiles were removed under reduced pressure and the residue was taken up in dilute aqueous acid (for composition see individual experiments in Supporting Information

Organocatalytic kinetic resolution of 1,5-dicarbonyl compounds through a retro-Michael reaction

• James Guevara-Pulido,
• Fernando González-Pérez,
• José M. Andrés and
• Rafael Pedrosa

Beilstein J. Org. Chem. 2025, 21, 473–482, doi:10.3762/bjoc.21.34

• low catalyst loadings and mild reaction conditions. This research focuses on the kinetic resolution of 1,5-dicarbonyl compounds using a retro-Michael reaction, co-catalyzed at room temperature with 20 mol % of the Jørgensen–Hayashi catalyst and PNBA. The study highlights the importance of conducting

• ] using 20 mol % of catalyst A and 20 mol % of p-nitrobenzoic acid (PNBA) as co-catalyst in different solvents at room temperature. The results obtained are summarized in Scheme 3 and Table 1. The progress of the reaction was monitored using thin-layer chromatography (TLC) and 1H NMR analysis of the

• excess reached is lower than at room temperature. Additionally, when the reaction mixture was stirred at −18 °C, no change was observed after 100 hours (entry 14, Table 2). These results led us to raise the reaction temperature to 31 °C (entries 17–20, Table 2). We observed that the retro-Michael

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

• Na2CO3 was ground in a mortar at room temperature for 3–5 min. Second, the reaction mixture was transferred into a quartz tube, heated to 50 °C (heating mantle) for 18 h, while being irradiated with blue LEDs under air-equilibrated conditions. In these conditions, product 3.3 was isolated in excellent

Electrochemical synthesis of cyclic biaryl λ³-bromanes from 2,2’-dibromobiphenyls

• Andrejs Savkins and
• Igors Sokolovs

Beilstein J. Org. Chem. 2025, 21, 451–457, doi:10.3762/bjoc.21.32

• required thermal decomposition of the diazonium salt to effect the cyclization. In the quest for mild (room temperature) and scalable conditions toward cyclic diaryl λ3-bromanes 1 we realized that bromanyl units possess leaving group abilities comparable to the diazonium moiety [1][15]. Hence, 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

• room temperature was the only difference with the pivaloyl group. Protecting the C-2 hydroxy group as ADMB ester yielded 1,2-trans glycosides in high yields. However, its participating mechanism is still unclear. So, we reserve our views on placing the use of ADMB as potential neighbouring group

Synthesis, structure, ionochromic and cytotoxic properties of new 2-(indolin-2-yl)-1,3-tropolones

• Yurii A. Sayapin,
• Eugeny A. Gusakov,
• Inna O. Tupaeva,
• Alexander D. Dubonosov,
• Igor V. Dorogan,
• Valery V. Tkachev,
• Anna S. Goncharova,
• Gennady V. Shilov,
• Natalia S. Kuznetsova,
• Svetlana Y. Filippova,
• Tatyana A. Krasnikova,
• Yanis A. Boumber,
• Alexey Y. Maksimov,
• Sergey M. Aldoshin and
• Vladimir I. Minkin

Beilstein J. Org. Chem. 2025, 21, 358–368, doi:10.3762/bjoc.21.26

• corresponding solution (1 mL) and the tetra-n-butylammonium salt (1 mL) solution were mixed directly in the cell and thoroughly stirred. Hence, the working concentrations of compounds 7 or 8 and anions was 2.5 × 10−5 mol L−1 and 5.0 × 10−5 mol L−1, respectively. All spectral experiments were performed at room

• temperature (23 °C). Chromatography was carried out on columns filled with Al2O3 of II–III degree of activity according to Brockmann. Melting points were determined on a Fisher-Johns melting point apparatus. 1,1,2-Trimethyl-1H-benzo[e]indolenine (2a, 98%, Alfa Aesar), 2,3,3-trimethyl-3H-benzo[g]indolenine (2b