On the photoluminescence in triarylmethyl-centered mono-, di-, and multiradicals

• Daniel Straub,
• Markus Gross,
• Mona E. Arnold,
• Julia Zolg and
• Alexander J. C. Kuehne

Beilstein J. Org. Chem. 2025, 21, 964–998, doi:10.3762/bjoc.21.80

• , there is a lack of understanding of why the absorption and photoluminescence of D3 symmetrical triphenylmethyl radicals are so weak in the visible spectrum. While it is understood that the functionalization with donor moieties breaks the D3 symmetry, the ϕ varies greatly among different donors and also

• by the heavy atom effect of iodine, that also allows intersystem crossing (ISC) between triplet states in the matrix and the emissive doublet states of 3I-PTM. Interestingly, functionalization of all three para-positions in TTM with chalcogens in the form of aryloxy- and aryl thioethers leads to

• functionalization with a much broader variety of donors (and even acceptors) than is possible through a radical-mediated nucleophilic aromatic substitution (SRN1, see also below) [3][46][47]. The I-TTM has a maximum emission at λem = 578 nm and a ϕ of 3% (in cyclohexane), indicating that the symmetry does not seem

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

• expect this metal-free protocol for alkene amino-oxygenation to find widespread use in both academic and industrial synthetic chemistry. Poor performers. Existing reports of intramolecular alkene functionalization reactions with nitreniums have focused on amino-trifluoroacetoxylations. We show the first

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

• powerful tool for the construction and functionalization of organic molecules and materials. Thus, the scientific community has focused on the design and study of new organic molecules that can be used as photocatalysts, replacing generally more expensive metal-based complexes [1][2][3]. Furthermore, there

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

• )–H functionalization/thiolation to deliver indane-fused pyrrolidines 43 in excellent yields (up to 92%). Strikingly, switching the solvent to acetonitrile completely suppresses carbene formation under identical conditions, redirecting the pathway toward an unconventional diazo reduction wherein aryl

• the critical role of reaction medium polarity in modulating reactive intermediates, offering a strategic lever to toggle between C–H functionalization and reductive manifolds in photochemical transformations. In 2024, the Cheng group developed a palladium/chiral norbornene (NBE)-catalyzed cyclization

Cu–Bpin-mediated dimerization of 4,4-dichloro-2-butenoic acid derivatives enables the synthesis of densely functionalized cyclopropanes

• Patricia Gómez-Roibás,
• Andrea Chaves-Pouso and
• Martín Fañanás-Mastral

Beilstein J. Org. Chem. 2025, 21, 877–883, doi:10.3762/bjoc.21.71

• are shown to undergo a rare dimerization process when reacted with bis(pinacolato)diboron under copper catalysis. The reaction provides densely functionalized products with excellent levels of chemo-, regio-, and diastereoselectivity. This high degree of functionalization makes these products

• ). We have studied this reaction and now report a catalytic methodology for the diastereoselective synthesis of these dimeric structures. The high degree of functionalization present in these molecules, which feature two ester groups, an aliphatic gem-dichloride and a dichloroalkene unit, offers ample

• opportunities for further functionalization. This is illustrated by their chemo- and diastereoselective conversion into densely functionalized cyclopropanes (Scheme 1c). Results and Discussion Based on our preliminary result, we started our study by exploring the reaction between ethyl 4,4-dichloro-2-butenoate

Synthesis and photoinduced switching properties of C₇-heteroatom containing push–pull norbornadiene derivatives

• Daniel Krappmann and
• Andreas Hirsch

Beilstein J. Org. Chem. 2025, 21, 807–816, doi:10.3762/bjoc.21.64

• little attention in the literature, with investigations largely limited to forward conversions [35]. Here, we present 2,3-heteroatom-incorporated NBD derivatives and compare their properties with those of previously published isocyclic derivatives. By utilizing push–pull functionalization and

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

• -system configuration promotes selective functionalization, enabling the synthesis of various complex products through a single transformation [17][18][19]. Therefore, allenes have become versatile intermediates in numerous transition-metal-catalyzed reactions [20][21]. Despite extensive studies on the

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

• ferrocene and ruthenocene via coupling reaction. This method provides an efficient and versatile synthetic approach for producing phosphorylated metallocenes but also aids in interpreting the regioselectivity and reactivity of C−H functionalization in unsymmetric metallocenes. They used a platinum electrode

Orthogonal photoswitching of heterobivalent azobenzene glycoclusters: the effect of glycoligand orientation in bacterial adhesion

• Leon M. Friedrich and
• Thisbe K. Lindhorst

Beilstein J. Org. Chem. 2025, 21, 736–748, doi:10.3762/bjoc.21.57

• functionalization of the ABF4 unit. The EE/ZE/EZ/ZZ isomeric mixture obtained after irradiation of the homobivalent photoswitchable glycocluster 6αMan3αMan 2 had to be determined by integration of the anomeric 1H/13C cross peak of the scaffold mannoside in the 1H,13C HSQC spectrum because the proton signals in the

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

• RNA. Key is the functionalization of the original N-(2-hydroxyethyl) moiety into a reactive handle providing a mild electrophile (LG), such as, e.g., N-(3-bromopropyl) or N-(3-mesyloxypropyl) [11]. Pepper aptamer reacts with different HBC derivatives. Chemical structures of the HBC derivatives used

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

• ligand L3 and the allylic electrophile 35. In contrast, a si-face attack leads to a higher-energy transition state due to significant steric repulsion. Enantioselective hydroallylation of vinyltrifluoromethyl compounds The direct functionalization of 1-trifluoromethylalkenes 38 through copper catalysis

• 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

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

• hydrolysis/amide bond formation sequence, and therefore they are suitable for the design of peptidomimetics. Further work is in progress in our laboratory to expand the scope of nucleophiles in the decarboxylative functionalization of malonic acid monoesters. Experimental General procedure for the

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

• proteins. By harnessing light to drive chemical transformations, photoredox techniques can facilitate the synthesis of antibody bioconjugates. This perspective will discuss the drive to develop and empower photoredox methods applied to antibody functionalization. Keywords: antibodies; bioconjugation

• ; bioorthogonality; chemoselectivity; late-stage functionalization; photochemistry; Introduction Antibodies represent increasingly important tools in several groundbreaking approaches to medical innovation, including basic biomedical research and therapy. One of the most critical requirements for the application of

• additionally generate an undesirable new stereocenter [26][27]. Few methods have been developed for the functionalization of tyrosine (Tyr) and tryptophan (Trp). With a low abundance (≈3%) in proteins, Tyr modifications are widely recognized for their ability to profoundly impact protein properties and

Total synthesis of (±)-simonsol C using dearomatization as key reaction under acidic conditions

• Xiao-Yang Bi,
• Xiao-Shuai Yang,
• Shan-Shan Chen,
• Jia-Jun Sui,
• Zhao-Nan Cai,
• Yong-Ming Chuan and
• Hong-Bo Qin

Beilstein J. Org. Chem. 2025, 21, 601–606, doi:10.3762/bjoc.21.47

• alcohol 19 was isolated in 89% yield. The copper-catalyzed replacement of the bromine substituent in 19 with a hydroxy group was achieved in the presence of a catalytic amount of oxalamide ligand I [13]. This transformation is critical for enabling further functionalization and the reaction conditions

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

• implementation often implies fewer purification steps to achieve the target molecules, leading to a reduction of waste, when compared to traditional “step by step” synthesis. Another advantage of MCRs is that by selecting appropriate starting materials, follow-up functionalization by, e.g., post-cyclization of

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

• on the regioselective electrophilic functionalization of this nitrogen heterocycle [15][16][17][18][19][20][21][22][23][24][25]. However, the vinylogous functionalization of 5-aminopyrazoles has not been described to the best of our knowledge (Figure 2). As a part of our ongoing interest in the

• functionalization of 5-aminopyrazoles [26], we decided to study 4-alkenyl-5-aminopyrazoles as nucleophiles in the vinylogous addition reaction to electrophiles. Herein, we report the regioselective and diastereoselective functionalization of 4-cyclohexenyl-5-aminopyrazoles using alkyl trifluoropyruvates [27][28][29

• starting materials to study the vinylogous functionalization with alkyl trifluoropyruvates. The synthesis of compounds 3 was accomplished by the reaction of cyclic ketones 1 and 5-aminopyrazoles 2 in the presence of acetic acid (Scheme 1) [30][31]. Cyclohexenones 1a–c provided the corresponding products

Synthesis of N-acetyl diazocine derivatives via cross-coupling reaction

• Thomas Brandt,
• Pascal Lentes,
• Jeremy Rudtke,
• Michael Hösgen,
• Christian Näther and
• Rainer Herges

Beilstein J. Org. Chem. 2025, 21, 490–499, doi:10.3762/bjoc.21.36

• ) N-acetyl diazocines have been synthesized and characterized. The synthesis has been performed from halogenated precursors and cross-coupling reactions for further functionalization. The reaction conditions of various cross-coupling reactions have been correspondingly adjusted. The arylation of the N

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

• require rethinking cavity design, but will be achieved predominantly by synthetic advances, for instance by the internal functionalization of cavities with bifunctionality – chemical groups that simultaneously activate nucleophiles and electrophiles or otherwise stabilize charged pairs. Herein, I argue

• assemble, modular functionalization of the periphery, sometimes internally projected [164][197][198], has been explored to alter the nature of the cavity (Figure 5C). However, the resulting groups tend to be flexible or loosely oriented and therefore contribute mainly effective molarity effects to

• , which can act as an oxidation catalyst (Figure 7C) [44]. The long-standing challenges of synthesis, stability, solubility and internal functionalization are beginning to be tackled, and the remainder of this Perspective will discuss specifics of these hard-earned advances and the opportunities they

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

• ], offering enhanced properties and efficacy [28][30][33][34][35]. Therefore, the advancement of simple, efficient methodologies for synthesizing o-carborane-fused heterocycles is critically needed. However, the limited number of synthetic strategies for carborane functionalization [36] continues to constrain

Identification and removal of a cryptic impurity in pomalidomide-PEG based PROTAC

• Bingnan Wang,
• Yong Lu and
• Chuo Chen

Beilstein J. Org. Chem. 2025, 21, 407–411, doi:10.3762/bjoc.21.28

• silica gel column chromatography. The LUMO and electrostatic charges of thalidomide and its derivatives by DFT calculation at the ωB97X-D/6-311+G** level. The synthetic route for iVeliparib-AP6. The conversion of byproduct 6 to 10 to facilitate its removal. Effects of the length and functionalization of

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

• or side reactivity in a scope of around 50 examples with yields ranging from 27 to 97 % compared to the use of blue-light (Scheme 3a) [20]. In this way, T. Rovis et al. have exploited their photocatalytic system on the functionalization of drug-like scaffolds with moderate to good yields (Scheme 3b

• such as zinc as proposed by Furuyama et al. [35]. In this way, the authors have developed a series of phthalocyanin zinc complexes with electron-rich sulfur atoms at the non-peripheral positions of the phthalocyanin ring. This functionalization allows the destabilization of the highest occupied

Synthesis and characterizations of highly luminescent 5-isopropoxybenzo[rst]pentaphene

• Islam S. Marae,
• Jingyun Tan,
• Rengo Yoshioka,
• Zakaria Ziadi,
• Eugene Khaskin,
• Serhii Vasylevskyi,
• Ryota Kabe,
• Xiushang Xu and
• Akimitsu Narita

Beilstein J. Org. Chem. 2025, 21, 270–276, doi:10.3762/bjoc.21.19

• -donating bis(methoxyphenyl)amino groups further improved the PLQY to 73%, displaying a mixed excitonic and charge-transfer character [22]. Additionally, the functionalization of BPP with two methyl benzoate groups enabled the development of hole-selective contact, which was applicable in significantly

Effect of substitution position of aryl groups on the thermal back reactivity of aza-diarylethene photoswitches and prediction by density functional theory

• Misato Suganuma,
• Daichi Kitagawa,
• Shota Hamatani and
• Seiya Kobatake

Beilstein J. Org. Chem. 2025, 21, 242–252, doi:10.3762/bjoc.21.16

• replacing the rotor pyridyl group of a hydrazone switch with a phenyl group afforded long-lived negative photochromic compounds [49]. In addition, Hecht and co-workers reported that the thermal stability of indigos can be tuned by N-functionalization [50][51]. They revealed that the introduction of electron

Visible-light-promoted radical cyclisation of unactivated alkenes in benzimidazoles: synthesis of difluoromethyl- and aryldifluoromethyl-substituted polycyclic imidazoles

• Yujun Pang,
• Jinglan Yan,
• Nawaf Al-Maharik,
• Qian Zhang,
• Zeguo Fang and
• Dong Li

Beilstein J. Org. Chem. 2025, 21, 234–241, doi:10.3762/bjoc.21.15

• substituted with halogen atoms (–F, –Cl, –Br) were also suitable for this transformation, efficiently giving the desired products in yields of 65–80% (3b, 3e–g), thus facilitating further functionalization possibilities. Notably, substrates with substituents at the sterically hindered 7-position of the

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

• catalysis to organic synthesis, focusing on recent developments in Cu-catalyzed electrochemical reaction categorized into four types: 1) C–H functionalization, 2) olefin addition, 3) decarboxylative functionalization, and 4) coupling reactions (Figure 3). This review aims to provide insight into the

• potential of copper-based electrochemical methodologies while also inspiring future research in this rapidly growing field. Review C–H Functionalization Site- and chemoselective C–H functionalization has emerged as a powerful platform for the formation of new C–C and C–heteroatom bonds, offering an

• functionalization of highly complex and diverse molecules, such as those of pharmaceuticals and natural products, has provided new retrosynthetic disconnections for complex compounds, contributing to improved resource efficiency [41][42][43][44][45][46]. Recently, the merging of C–H activation and electrochemistry