Palladium-catalyzed regioselective C1-selective nitration of carbazoles

• Vikash Kumar,
• Jyothis Dharaniyedath,
• Aiswarya T P,
• Sk Ariyan,
• Chitrothu Venkatesh and
• Parthasarathy Gandeepan

Beilstein J. Org. Chem. 2025, 21, 2479–2488, doi:10.3762/bjoc.21.190

• 2s (36%) and 2s' (15%). It is worth noting that under the standard reaction conditions, indole substrates 1t and 1u failed to afford the desired products 2t and 2u. Encouraged by these results, and to further demonstrate the synthetic utility of the established reaction protocol, we carried out a

• carbazoles. Scope of the method. Reaction conditions: 1 (0.2 mmol, 1.0 equiv), Pd2(dba)3 (0.02 mmol, 10 mol %), AgNO3 (0.24 mmol, 1.2 equiv), and 1,4-dioxane (2.0 mL) at 120 °C for 24 h. a10 mol % of Pd(OAc)2 was used instead of Pd2(dba)3. Gram-scale synthesis, directing group removal, and synthetic utility

Pathway economy in cyclization of 1,n-enynes

• Hezhen Han,
• Wenjie Mao,
• Bin Lin,
• Maosheng Cheng,
• Lu Yang and
• Yongxiang Liu

Beilstein J. Org. Chem. 2025, 21, 2260–2282, doi:10.3762/bjoc.21.173

• synthetic intermediates, and used to successfully modify diverse bioactive scaffolds via late-stage functionalization, collectively demonstrating the method’s synthetic utility. In 2025, the Das group developed a palladium-catalyzed cycloisomerization of 2-alkynylbenzoate-cyclohexadienone that enables

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

• methanol. The driving force of this process is the formation of an aromatic thiophene system. To demonstrate the practicability and synthetic utility of this method for the synthesis of benzo[4,5]thieno[3,2-b]pyrrole derivatives, several transformations of compound 3b were carried out (Scheme 4

Oxetanes: formation, reactivity and total syntheses of natural products

• Peter Gabko,
• Martin Kalník and
• Maroš Bella

Beilstein J. Org. Chem. 2025, 21, 1324–1373, doi:10.3762/bjoc.21.101

• is to provide a comprehensive review of oxetanes in terms of their preparation and synthetic utility. Because multiple reviews of similar formats covering literature up to late 2015 have already been published [12][32][33][34], we will discuss primarily the most recent advancements since the year

• , Howell et al. recently disclosed a general method for the synthesis of 2-halomethylideneoxetanes through halogenation of 2-methylideneoxetanes using N-halosuccinimides, and illustrated their synthetic utility by Suzuki–Miyaura, Sonogashira and Buchwald–Hartwig coupling reactions [53]. In addition to Cu

Recent advances in amidyl radical-mediated photocatalytic direct intermolecular hydrogen atom transfer

• Hao-Sen Wang,
• Lin Li,
• Xin Chen,
• Jian-Li Wu,
• Kai Sun,
• Xiao-Lan Chen,
• Ling-Bo Qu and
• Bing Yu

Beilstein J. Org. Chem. 2025, 21, 1306–1323, doi:10.3762/bjoc.21.100

• concurrent generation of byproduct 46. Subsequent trapping of radical 4 by HRP-9 leads to the generation of product 69. This methodology demonstrates a broad substrate scope and exhibits significant synthetic utility, particularly for the generation of products 70, 71, and 72 with yields ranging from 54% to

Recent advances in oxidative radical difunctionalization of N-arylacrylamides enabled by carbon radical reagents

• Jiangfei Chen,
• Yi-Lin Qu,
• Ming Yuan,
• Xiang-Mei Wu,
• Heng-Pei Jiang,
• Ying Fu and
• Shengrong Guo

Beilstein J. Org. Chem. 2025, 21, 1207–1271, doi:10.3762/bjoc.21.98

Synthesis of β-ketophosphonates through aerobic copper(II)-mediated phosphorylation of enol acetates

• Alexander S. Budnikov,
• Igor B. Krylov,
• Fedor K. Monin,
• Valentina M. Merkulova,
• Alexey I. Ilovaisky,
• Liu Yan,
• Bing Yu and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2025, 21, 1192–1200, doi:10.3762/bjoc.21.96

• oxide gave the corresponding product 3s in 58% yield, although earlier 3s wasn’t observed in an analogous reaction when Mn(acac)3 was used as an oxidant [71]. The synthetic utility of the developed protocol was demonstrated by performing the model reaction on a 6 mmol scale (Scheme 3), product 3a was

Light-enabled intramolecular [2 + 2] cycloaddition via photoactivation of simple alkenylboronic esters

• Lewis McGhie,
• Hannah M. Kortman,
• Jenna Rumpf,
• Peter H. Seeberger and
• John J. Molloy

Beilstein J. Org. Chem. 2025, 21, 854–863, doi:10.3762/bjoc.21.69

• , bottom). Despite the additional substituent, the reaction was tolerated, albeit with decreased diastereoselectivity in comparison to previous alkenylboronic ester examples 4b–d. To demonstrate the synthetic utility of the generated small 3D fragments and complement existing [2 + 2] strategies via direct

• be derivatized to demonstrate the synthetic utility of the process. Although reactivity is currently limited to intramolecular quenching, it is envisaged the developed insights will serve as a blueprint for future endeavors to achieve sensitization using high energy photocatalysts, especially when

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

• its synthetic utility and potential applicability in complex molecule synthesis. Results and Discussion We began by optimizing the hydrocyanation of allene 1a using DIBAL-H as the hydride source and p-toluenesulfonyl cyanide as the cyanating reagent (Scheme 2). Under previously established conditions

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

• advancement requires establishing catalytic systems that effectively utilize chiral secondary organocopper species, making the understanding of their nature and behavior crucial for expanding the synthetic utility of this transformation. The purpose of this review is to present recent procedures for

• reactions with various chiral cycloallylic phosphates 17, which consistently yielded the corresponding SN2' products 18 with high stereoselectivity. The synthetic utility and broad applicability of this methodology was prominently demonstrated through the total synthesis of biologically important natural

• construct non-benzylic and non-allylic CF3-substituted C(sp3) stereogenic centers. The synthetic utility of this allylation process was demonstrated through the facile functionalization of the allylic moiety in the enantioenriched product 41, providing access to optically active CF3-containing compounds

Recent advances in organocatalytic atroposelective reactions

• Henrich Szabados and
• Radovan Šebesta

Beilstein J. Org. Chem. 2025, 21, 55–121, doi:10.3762/bjoc.21.6

• (Scheme 61) [91]. After testing a considerable number of substrates, the authors achieved excellent yields and enantioselectivities. The synthetic utility of this approach stems from being able to skip additional reaction steps and thus omit reagents used in those steps, leading to increased efficiency

Non-covalent organocatalyzed enantioselective cyclization reactions of α,β-unsaturated imines

• Sergio Torres-Oya and
• Mercedes Zurro

Beilstein J. Org. Chem. 2024, 20, 3221–3255, doi:10.3762/bjoc.20.268

• evaluate the synthetic utility of this methodology, derivative 39e was reduced using BF3·OEt2 and Et3SiH leading to 41 in a good yield and moderate diastereoselectivity (Scheme 14). In 2017, Li’s group developed a chiral (DHQ)2PHAL-catalyzed [2 + 4] annulation reaction of cyclic 1-azadiene 14 with γ-nitro

C–H Trifluoromethylthiolation of aldehyde hydrazones

• Victor Levet,
• Balu Ramesh,
• Congyang Wang and
• Tatiana Besset

Beilstein J. Org. Chem. 2024, 20, 2883–2890, doi:10.3762/bjoc.20.242

• , alkenes) and halogens allowing an array of post-functionalization reactions. Finally, the trifluoromethylthiolation of molecules derived from compounds of interest was achieved to illustrate the synthetic utility of the method. Hence, the desired products 2v–x were efficiently isolated. To get more

• AgSCF3. Finally, to further illustrate the synthetic utility of the trifluoromethylthiolated hydrazones, product 2g was further functionalized. In the presence of 4-methylboronic acid, the arylation of 2g occurred and the expected product was isolated in 72% yield with the SCF3-hydrazone motif remaining

Synthesis of spiroindolenines through a one-pot multistep process mediated by visible light

• Francesco Gambuti,
• Jacopo Pizzorno,
• Chiara Lambruschini,
• Renata Riva and
• Lisa Moni

Beilstein J. Org. Chem. 2024, 20, 2722–2731, doi:10.3762/bjoc.20.230

• simultaneous insertion of an isocyanide into the N–H bond. This evidence shows that 5 was able to be oxidized but the iminium ion formed was not stable enough to take part in the subsequent reaction, preferring to hydrolytically open. In order to test the synthetic utility of this procedure we also carried out

Transition-metal-free decarbonylation–oxidation of 3-arylbenzofuran-2(3H)-ones: access to 2-hydroxybenzophenones

• Bhaskar B. Dhotare,
• Seema V. Kanojia,
• Chahna K. Sakhiya,
• Amey Wadawale and
• Dibakar Goswami

Beilstein J. Org. Chem. 2024, 20, 2655–2667, doi:10.3762/bjoc.20.223

• NMR spectrum was consistent with the generation of tetrahydrofuran-2-hydroperoxide in THF, and was similar to the NMR reported earlier [25]. Further, the reaction of 3ba was scaled up to demonstrate the synthetic utility of our protocol. The reactions involving hydroperoxides are known to be difficult

Base-promoted cascade recyclization of allomaltol derivatives containing an amide fragment into substituted 3-(1-hydroxyethylidene)tetronic acids

• Andrey N. Komogortsev,
• Constantine V. Milyutin and
• Boris V. Lichitsky

Beilstein J. Org. Chem. 2024, 20, 2585–2591, doi:10.3762/bjoc.20.217

• purification. The synthetic utility of the prepared tetronic acids was demonstrated by further transformations at the hydroxyethylidene fragment. The structures of one obtained tetronic acid and one product of derivatization were confirmed by X-ray analysis. Keywords: allomaltol; base-promoted recyclization

• purification procedure are the advantages of the considered method. The synthetic utility of obtained tetronic acids was demonstrated by preparation of enamine and enehydrazine derivatives. The structures of one target tetronic acid and synthesized enehydrazine were established by X-ray analysis. Experimental

A review of recent advances in electrochemical and photoelectrochemical late-stage functionalization classified by anodic oxidation, cathodic reduction, and paired electrolysis

• Nian Li,
• Ruzal Sitdikov,
• Ajit Prabhakar Kale,
• Joost Steverlynck,
• Bo Li and
• Magnus Rueping

Beilstein J. Org. Chem. 2024, 20, 2500–2566, doi:10.3762/bjoc.20.214

Asymmetric organocatalytic synthesis of chiral homoallylic amines

• Nikolay S. Kondratyev and
• Andrei V. Malkov

Beilstein J. Org. Chem. 2024, 20, 2349–2377, doi:10.3762/bjoc.20.201

• 28–96%, whereas enantioselectivities remained modest (20–78% ee). To illustrate the synthetic utility of the products, a double Cu(acac)2-catalysed aziridination of the model substrate 109 was carried out using a large excess of PhI=NNs reagent (15 equiv, Ns = nosyl) to afford diastereoselectively

• methallyl derivative 130, the stereoselectivity dropped to a modest level (dr 5:1, ee 60%, yield 60%), whereas higher allyl homologues such as phenyl and benzyl proved to be inactive (Scheme 26). The synthetic utility of the resulting homoallylic N-benzophenone imines 131 was illustrated on a laboratory

Heterocycle-guided synthesis of m-hetarylanilines via three-component benzannulation

• Andrey R. Galeev,
• Maksim V. Dmitriev,
• Alexander S. Novikov and
• Andrey N. Maslivets

Beilstein J. Org. Chem. 2024, 20, 2208–2216, doi:10.3762/bjoc.20.188

• ) demonstrates the synthetic utility of the developed method. Keywords: aniline; benzannulation; condensation; 1,3-diketone; Hammett constants; terphenyl; Introduction The aniline moiety is omnipresent in the synthetic chemistry with applications ranging from building blocks to catalysis [1][2][3][4]. Among

Diastereoselective synthesis of highly substituted cyclohexanones and tetrahydrochromene-4-ones via conjugate addition of curcumins to arylidenemalonates

• Deepa Nair,
• Abhishek Tiwari,
• Banamali Laha and
• Irishi N. N. Namboothiri

Beilstein J. Org. Chem. 2024, 20, 2016–2023, doi:10.3762/bjoc.20.177

• [26][29]. In order to demonstrate the synthetic utility of our methodology, we performed a scale-up reaction with representative starting materials, viz. 1a and 2b on a 1.0 mmol scale (Scheme 3). The reaction required slightly more time and resulted in the corresponding double and triple Michael

Regioselective alkylation of a versatile indazole: Electrophile scope and mechanistic insights from density functional theory calculations

• Pengcheng Lu,
• Luis Juarez,
• Paul A. Wiget,
• Weihe Zhang,
• Krishnan Raman and
• Pravin L. Kotian

Beilstein J. Org. Chem. 2024, 20, 1940–1954, doi:10.3762/bjoc.20.170

• indazoles would provide greater synthetic utility for this valuable heterocycle. These examples suggest a common intermediate such as methyl 5-bromo-1H-indazole-3-carboxylate (6) could be used to generate such compounds. An alkylation strategy that uses the vast array of commercially available alcohols as

Solvent-dependent chemoselective synthesis of different isoquinolinones mediated by the hypervalent iodine(III) reagent PISA

• Ze-Nan Hu,
• Yan-Hui Wang,
• Jia-Bing Wu,
• Ze Chen,
• Dou Hong and
• Chi Zhang

Beilstein J. Org. Chem. 2024, 20, 1914–1921, doi:10.3762/bjoc.20.167

• hexafluoro-2-propanol led to 3-substituted isoquinolinones. The solvent-dependent chemoselective synthesis of isoquinolinone derivatives is interesting and unprecedented. Further research on synthetic utility of PISA, a unique zwitterionic hypervalent iodine(III) reagent, is underway in our laboratory

Electrochemical radical cation aza-Wacker cyclizations

• Sota Adachi and
• Yohei Okada

Beilstein J. Org. Chem. 2024, 20, 1900–1905, doi:10.3762/bjoc.20.165

• these cyclizations would be of great help to expand their synthetic utility. Described herein are electrochemical aza-Wacker cyclizations under acidic conditions, which are expected to proceed via radical cations. Results and Discussion The present work began by examining the electrochemical aza-Wacker

Synthesis of 4-functionalized pyrazoles via oxidative thio- or selenocyanation mediated by PhICl₂ and NH₄SCN/KSeCN

• Jialiang Wu,
• Haofeng Shi,
• Xuemin Li,
• Jiaxin He,
• Chen Zhang,
• Fengxia Sun and
• Yunfei Du

Beilstein J. Org. Chem. 2024, 20, 1453–1461, doi:10.3762/bjoc.20.128

• pyrazole derivatives. Further investigations of the synthetic utility of this approach are currently ongoing in our lab. Representative pyrazoles with pharmacological activities and S/Se-containing pharmaceutical molecules. Approaches for thio/selenocyanation of the pyrazole skeleton. PhICl2/NH4SCN

Synthesis of 1,2,3-triazoles containing an allomaltol moiety from substituted pyrano[2,3-d]isoxazolones via base-promoted Boulton–Katritzky rearrangement

• Constantine V. Milyutin,
• Andrey N. Komogortsev and
• Boris V. Lichitsky

Beilstein J. Org. Chem. 2024, 20, 1334–1340, doi:10.3762/bjoc.20.117

• cyclization with participation of hydrazine and carbonyl functions leads to pyrazolylisoxazole D. Finally, condensation with second equivalent of hydrazine results in the target hydrazone 6. The synthetic utility of obtained 1,2,3-triazoles is demonstrated by its further derivatization. So, alkylation by MeI