Streamlined modular synthesis of saframycin substructure via copper-catalyzed three-component assembly and gold-promoted 6-endo cyclization

• Asahi Kanno,
• Ryo Tanifuji,
• Satoshi Yoshida,
• Sota Sato,
• Saori Maki-Yonekura,
• Kiyofumi Takaba,
• Jungmin Kang,
• Kensuke Tono,
• Koji Yonekura and
• Hiroki Oguri

Beilstein J. Org. Chem. 2025, 21, 226–233, doi:10.3762/bjoc.21.14

• degassed solvent and light-shielding flask, the oxidative conversion of 12 to the imidate 18 proceeded smoothly. Notably, the transient intermediate 18, exhibiting a sky-blue fluorescence, further underwent a ring opening to afford the tetracyclic 14 with the simultaneous regeneration of both a nitrile and

• , excited at 375 nm): 0.07 (c = 10 μM). Emission image was captured under UV light (365 nm, c = 100 μM in CHCl3). Strategies for the construction of the pentacyclic core scaffold of saframycin A (1). (a) Biosynthetic machinery catalyzed by an NRPS module SfmC. (b) Total syntheses utilizing the Pictet

Hydrogen-bonded macrocycle-mediated dimerization for orthogonal supramolecular polymerization

• Wentao Yu,
• Zhiyao Yang,
• Chengkan Yu,
• Xiaowei Li and
• Lihua Yuan

Beilstein J. Org. Chem. 2025, 21, 179–188, doi:10.3762/bjoc.21.10

• , when G2 and zinc salt were mixed together in a 1:1 molar ratio, results from dynamic light scattering experiments showed that the average hydrodynamic diameter (Dh) was 524 nm, and no particles of discernible size were observed for a mixture of the macrocycle H1 and G2, or H1 and the salt, whereas with

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

• products and drugs has proven to be useful in these reactions. As shown in Figure 7, the photocatalyst sodium anthraquinone-2,7-disulfonate (AQDS) is excited by 395 nm light to form AQDS* and undergoes electron transfer with arylalkanes 20 to generate an ion-radical pair (AQDS•−, 20•+). This ion radical

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

• and sulfur dioxide afforded vinyl sulfones with excellent regio- and stereoselectivity (Scheme 9) [22]. The authors used DABCO(SO2)2 to generate sulfur dioxide, and visible light irradiation and the mandatory presence of a photocatalyst for this transformation suggested a radical mechanism. The

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

• astounding enantioselectivities. Both, light and organocatalyst proved crucial for the reaction. The photochemical aspect isomerizes the double bond to (Z)-configuration, and CPA stabilizes the structure whilst mediating the cyclization. The wavelength of 405 nm was chosen so that only the starting material

• , not the organocatalyst nor the product being formed, effectively absorb the light. An atroposelective C–H amination was done with the help of SPINOL-derived chiral phosphoric acids C51, C40, and C42 (Scheme 66) [96]. It was a reaction of naphthalenyldiazene carboxylates 222 with derivatives of

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

• broadening their potential applications in drug delivery and nanotechnology. Our findings shed light on the unique capabilities of polysarcosine-based polymers, paving the way for further exploration and harnessing of their distinctive properties in biomedical research. Keywords: biodegradable; poly(benzyl

Emerging trends in the optimization of organic synthesis through high-throughput tools and machine learning

• Pablo Quijano Velasco,
• Kedar Hippalgaonkar and
• Balamurugan Ramalingam

Beilstein J. Org. Chem. 2025, 21, 10–38, doi:10.3762/bjoc.21.3

• with feedback DOE facilitated the rapid identification of appropriate solvents. Notably, the use of DMSO, DMF, and pyridine led to an enhanced yield of the monoalkylated product. An experimental setup was developed for single-droplet studies of visible-light photoredox catalysis using an oscillatory

• light [40]. The design allows the screening to be more material- and time-efficient in the optimization of both continuous variables (e.g., temperature and residence time) and discrete variables (e.g., catalyst, base). Pieber et al. [46] reported the application of a segmental flow reactor for

• . Photochemical reactions require uniform light penetration of the reaction mixture, and flow setups with uniform path lengths would be ideal for such reactions. A self-optimizing continuous-flow reactor was designed by Poscharny et al. [59] for [2 + 2]-cycloaddition reactions promoted by light. The optimization

Synthesis, structure and π-expansion of tris(4,5-dehydro-2,3:6,7-dibenzotropone)

• Yongming Xiong,
• Xue Lin Ma,
• Shilong Su and
• Qian Miao

Beilstein J. Org. Chem. 2025, 21, 1–7, doi:10.3762/bjoc.21.1

• the colorless crystal, two of these [5]helicenoid moieties display P and M helix structures respectively, whereas the third moiety (colored in light blue) adopts a structure with approximate plane symmetry, recognized as a transition state for the enantiomerization of helicenes. The central benzene

• to Cs-1 (4.37 eV) as calculated at the B3LYP/6-311++G(d,p) level of DFT. The reduced HOMO–LUMO gap of C2-1 can be attributed to the greater conjugation in the essentially flat dibenzotropone moiety. This finding aligns with the fact that the yellow crystal of C2-1 absorbs light of a longer wavelength

• represent the helicity of the three [5]helicenoid moieties. The geometry of 3 deviates from ideal C2 symmetry, as the light blue moiety of 3 (top view in Figure 3) is shaped like a saddle. However, the 1H NMR spectrum of 3 shows only 12 different signals in the aromatic region, indicating a two-fold

Synthesis, characterization, and photophysical properties of novel 9‑phenyl-9-phosphafluorene oxide derivatives

• Shuxian Qiu,
• Duan Dong,
• Jiahui Li,
• Huiting Wen,
• Jinpeng Li,
• Yu Yang,
• Shengxian Zhai and
• Xingyuan Gao

Beilstein J. Org. Chem. 2024, 20, 3299–3305, doi:10.3762/bjoc.20.274

• phosphine oxide (PO) groups have recently received considerable attention for their high thermal stability and unique optoelectronic features, and thus being widely applied in organic light-emitting diodes (OLEDs) [1][2]. To date, tremendous efforts have been devoted to the development of a variety of high

Synthesis of acenaphthylene-fused heteroarenes and polyoxygenated benzo[j]fluoranthenes via a Pd-catalyzed Suzuki–Miyaura/C–H arylation cascade

• Merve Yence,
• Dilgam Ahmadli,
• Damla Surmeli,
• Umut Mert Karacaoğlu,
• Sujit Pal and
• Yunus Emre Türkmen

Beilstein J. Org. Chem. 2024, 20, 3290–3298, doi:10.3762/bjoc.20.273

• fluorescent chemosensors and probes [4][5][6], as well as materials for applications in organic light-emitting diodes (OLEDs) [7][8][9], organic field-effect transistors (OFETs) [10], and perovskite solar cells [11]. In this respect, replacing either one or more of the carbons or rings of a fluoranthene with

Reactivity of hypervalent iodine(III) reagents bearing a benzylamine with sulfenate salts

• Beatriz Dedeiras,
• Catarina S. Caldeira,
• José C. Cunha,
• Clara S. B. Gomes and
• M. Manuel B. Marques

Beilstein J. Org. Chem. 2024, 20, 3281–3289, doi:10.3762/bjoc.20.272

• . A deeper analysis of the composition of the crude mixture revealed the presence of sulfide 3a and disulfide 7a, which formation might probably result from an oxidative reaction involving species generated from 2 sulfenate molecules. A further experiment was carried out in the absence of light. Under

• reaction mechanism that would support both the obtained yields and the formation of unexpected species. As mentioned above, the presence of light influences the reaction outcome. When the reaction was carried out in the absence of light, only 4a, 3a, and 7a were isolated (under these conditions, there was

• a high decrease in the isolated amount of 3a, compared to the same experiment carried out in the presence of light, from 20% to 2% yield). Considering the potential occurrence of a radical pathway, additional experiments were conducted in the presence of galvinoxyl and TEMPO, powerful radical

Giese-type alkylation of dehydroalanine derivatives via silane-mediated alkyl bromide activation

• Perry van der Heide,
• Michele Retini,
• Fabiola Fanini,
• Giovanni Piersanti,
• Francesco Secci,
• Daniele Mazzarella,
• Timothy Noël and
• Alberto Luridiana

Beilstein J. Org. Chem. 2024, 20, 3274–3280, doi:10.3762/bjoc.20.271

• photochemistry has introduced new ways of generating radicals like photoredox catalysis and via electron donor–acceptor (EDA) complexes [10][11][12][13]. These advances, coupled with modern electrochemical methods, chemical reactor engineering and light emitting diodes (LED), have eliminated the need for thermal

Efficient synthesis of fluorinated triphenylenes with enhanced arene–perfluoroarene interactions in columnar mesophases

• Yang Chen,
• Jiao He,
• Hang Lin,
• Hai-Feng Wang,
• Ping Hu,
• Bi-Qin Wang,
• Ke-Qing Zhao and
• Bertrand Donnio

Beilstein J. Org. Chem. 2024, 20, 3263–3273, doi:10.3762/bjoc.20.270

• ] in combination with tunable absorption and emission of visible light. Polar nematic phase [23] and chiral columnar phase materials [24] based on polar fluorobenzene rings have also recently emerged as interesting new classes of fluorous materials, revealing their enormous potential in the high-tech

• been studied in various solutions and thin film: G66 emitted green light in solution with an absolute photoluminescent quantum yield of ca. 33%. Results and Discussion Synthesis and characterization We have recently generalized a very efficient “palladium-free” synthesis for the preparation of a

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

• ; Pseudomonas; Suberea; total synthesis; Introduction The marine environment covers over two thirds of the earth’s surface and it encompasses a wide range of complex ecosystems that are highly variable in their physical attributes including pressure, salinity, temperature, and light availability. Both flora

Multicomponent reactions driving the discovery and optimization of agents targeting central nervous system pathologies

• Lucía Campos-Prieto,
• Aitor García-Rey,
• Eddy Sotelo and
• Ana Mallo-Abreu

Beilstein J. Org. Chem. 2024, 20, 3151–3173, doi:10.3762/bjoc.20.261

• other approaches such as visible light, microwaves, heterogeneous catalysis, and ultrasound [12][13][14][15]. Due to its versatility, one of the most prevalent of these MCRs is the Ugi reaction [16]. This reaction generally combines an isocyanide with an acid, an amine, and an aldehyde or ketone to

Controlled oligomerization of [1.1.1]propellane through radical polarity matching: selective synthesis of SF₅- and CF₃SF₄-containing [2]staffanes

• Jón Atiba Buldt,
• Wang-Yeuk Kong,
• Yannick Kraemer,
• Masiel M. Belsuzarri,
• Ansh Hiten Patel,
• James C. Fettinger,
• Dean J. Tantillo and
• Cody Ross Pitts

Beilstein J. Org. Chem. 2024, 20, 3134–3143, doi:10.3762/bjoc.20.259

• in the absence of light. Note that recent work from the laboratories of Cahard and Bizet [50] suggests that autoxidation of the ethereal solvent could serve as one possible explanation for initial formation of SF5 radicals in the absence of light to initiate a radical chain reaction. It is also well

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

• to absorb significant amounts of visible light photons, which allows them to reach an excited state. The excited porphyrin molecule is likely to undergo energy transfer (ET; photosensitization) or single-electron transfer (SET; photoredox catalysis) to substrate molecules (Figure 13). In

• (1O2) finds many applications in photochemistry and photobiology, e.g., for wastewater treatment, fine chemical synthesis, and photodynamic therapy (PDT) [79][80][81][82][83]. Additionally, after light excitation, porphyrins can also oxidize a substrate by accepting electrons from a substrate molecule

• porphyrin catalyst, amine, aldehyde, EDA, or light source – completely halted the reaction, resulting in no product formation. The further study found that porphyrins with both electron-withdrawing and electron-donating substituents at the meso-positions were catalytically active. Additionally, among

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

• extensively investigated allylation with allyltrichlorosilane [58][59]. In light of the excellent reactivity and promising selectivity displayed by catalyst 8 for the model reaction, we proceeded to evaluate its ability to enantioselectively promote the allenylation of various aldehydes (Scheme 5). The

Extension of the π-system of monoaryl-substituted norbornadienes with acetylene bridges: influence on the photochemical conversion and storage of light energy

• Robin Schulte,
• Dustin Schade,
• Thomas Paululat,
• Till J. B. Zähringer,
• Christoph Kerzig and
• Heiko Ihmels

Beilstein J. Org. Chem. 2024, 20, 3061–3068, doi:10.3762/bjoc.20.254

• up to 8 h at room temperature. Furthermore, the norbornadienes were transformed quantitatively into their quadricyclane photoproducts by irradiation with green light (520 nm) in the presence of a photosensitizer. Keywords: light energy conversion; photochemistry; photochromism; quadricyclanes

• promising approach towards storage of solar energy is represented by the molecular solar thermal (MOST) energy storage systems, which have the ability to convert and store (sun)light energy in reversible photochemical reactions. Specifically, this approach is based on photoactive compounds that are

• converted into photoisomers with higher energy upon absorption of light. In turn, this reaction is reversible, thus allowing to release the stored chemical energy as heat in a specifically triggered back reaction [7][8][10][11][12][13]. For a practicable MOST system, some key parameters have to be ensured

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

• approaches have already facilitated the discovery of numerous new bioactive molecules [29][30][31][32][33][34][35][36] and shed light on the scope of past discovery efforts by uncovering select oversampled/underexplored niches in the natural product chemical spaces [37]. While nonribosomal peptides (NRP

• unacceptably high rediscovery rates, because BGF has nearly exhausted the rather limited chemical space it can access. In light of BGF’s decreasing return-on-investment, scientists have developed new natural product discovery methods to tap into the microbial biosynthetic diversity of the “uncultured majority

Cyclodextrin-based rotaxanes for polymer materials: challenge on simultaneous realization of inexpensive production and defined structures

• Yosuke Akae

Beilstein J. Org. Chem. 2024, 20, 3026–3049, doi:10.3762/bjoc.20.252

• visible-light irradiation or heating, CD was moved back to the azobenzene moiety, and the entire process was reversible. This system was further developed in 2005 by introducing bipyridinium moieties to implement the selective transfer of the wheel via heating or light irradiation (Figure 5B) [57]. During

• α-CD-based rotaxane comprising a stilbene axle that was synthesized by the Suzuki coupling reaction to light irradiation (Figure 6, right) [58]. In this structure, α-CD was first located on the trans-stilbene moiety, after which it moved to the benzene ring moiety via the cis-isomerization of the

• stilbene framework by 335 nm light irradiation before returning to the stilbene moiety via trans-isomerization induced by the 280 nm light irradiation; this system is also reversible. The change in the local position of CD is significantly reflected in the ICD behavior of this system. Kodaka and co-workers

Tunable full-color dual-state (solution and solid) emission of push–pull molecules containing the 1-pyrindane moiety

• Anastasia I. Ershova,
• Sergey V. Fedoseev,
• Konstantin V. Lipin,
• Mikhail Yu. Ievlev,
• Oleg E. Nasakin and
• Oleg V. Ershov

Beilstein J. Org. Chem. 2024, 20, 3016–3025, doi:10.3762/bjoc.20.251

• materials [14][20][21][22][23][24][25][26][27][28][29][30][31][32][33]. For example, organic π-systems whose main structural unit is stilbazole are used as active compounds in organic light-emitting diodes (OLEDs) [20], dye-sensitized solar cells (DSSCs) [21], nonlinear optics (NLO) materials [22][23

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

• in Kwon’s review [34]. Cu-catalyzed oxygen atom transfer with TBHP were discussed in the review [35]. The review by Xiao considered visible light-driven C–C bond cleavage enabled with organic peroxides [36]. This comprehensive review summarizes all ever published studies on radical peroxidation with

• photocatalytic system under visible light irradiation (443 nm) [56]. Peroxidation of β-ketoesters, cyanoacetic esters, and malonic esters 37 was performed using the TBAI/TBHP system (Scheme 15) [57]. The highest product yields in the TBAI-catalyzed peroxidation were achieved with malonic acid esters, in contrast

• in situ-generated Cu(I) complexes was developed (Scheme 23) [43]. 2-Phenylbutane (64) was converted into peroxide 65 in a 70% yield with 4% ee. A visible light-induced direct decarboxylative peroxidation of carboxylic acids 66 with the formation of peroxides 67 under metal-free conditions using Mes

4,6-Diaryl-5,5-difluoro-1,3-dioxanes as chiral dopants for liquid crystal compositions

• Maurice Médebielle,
• Peer Kirsch,
• Jérémy Merad,
• Carolina von Essen,
• Clemens Kühn and
• Andreas Ruhl

Beilstein J. Org. Chem. 2024, 20, 2940–2945, doi:10.3762/bjoc.20.246

• chemistry [1][2][3]. In particular, cholesteric, i.e., chiral nematic, liquid crystals (LCs) are attractive for many display applications due to their chiroptical characteristics as well as the selective reflection of light giving rise to Bragg interference colors [4]. Cholesteric LCs can be obtained either

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

• position of quinoline N-oxides and pyridine N-oxides, utilizing hypervalent iodine salts as the arylation reagents. The reaction was facilitated by visible light in conjunction with a photocatalyst. The absence of either the photocatalyst or light resulted in only trace amounts of the product, underscoring

• mechanism by adding 2 equivalents of TEMPO to the reaction mixture. The absence of the desired product indicated the involvement of a radical pathway in the process. The proposed reaction mechanism begins with the activation of eosin Y by visible light from 5 W blue LEDs, transitioning it to its excited

• photosensitizer and DIPEA was effective as a base (Scheme 12). The reaction yielded the E-isomers in a solvent mixture of methanol/water 5:1 under blue LED light (467 nm) irradiation in good yields. Various DAIRs substituted at different positions were found to be suitable for the reaction giving the respective