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

• ): CF2C6F5I (19 µL, 0.11 mmol) was syringed into a glass ampoule containing anthracene (10 mg, 0.056 mmol) and copper powder (11 mg, 0.17 mmol) dissolved in DMSO, and degassed by a freeze-pump-thaw technique (3 × 10 min). The ampoule was then heated in an oil bath at 160 °C for 24 h. The reaction contents

• -10-bis(perfluorobenzyl)anthracene were mounted in a paratone oil on glass fiber rods glued to a small copper wire. X-ray diffraction data were collected at ChemMatCARS (CARS = consortium for advanced radiation sources) sector 15-B at the Advanced Photon Source (Argonne National Laboratory). The data

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

• provided the corresponding amino-substituted N-acetyl diazocine 21 (Scheme 1). Another option for carbon–heteroatom bond formation reactions are copper-catalyzed Ullmann-type reactions, which have already been applied to the parent diazocine [36][37]. The attempted synthesis of azide-functionalized N

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

• shield above each jar holder allows for irradiation of the reaction glass vessels from above using powerful LED lamps. First, photomechanochemistry facilitated the copper-photocatalyzed ATRA of sulfonyl chlorides and styrenes under fully aerobic conditions (Scheme 11A), a feature unattainable in

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

• ][344][345], which show early promise for low-symmetry cavities with catalytic potential [42][43][44][340]. Notably, Otte has used semi-stepwise self-assembly via imine formation/reduction to access a robust organic cage with reduced-symmetry and internal functionality able to chelate a copper(I) ion

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

• [Os(tpy)2]2+/red-light irradiation system well-suited for large-scale manufacturing. In this way, the authors have also tested different osmium complexes in various well-established photocatalyzed reactions such as copper, palladium, cobalt, and nickel metallophotoredox couplings using red light

• . While transition metals such as copper, palladium, cobalt, and nickel are well-established in catalyzed cross-coupling reactions, J. Cornella et al. have highlighted the reactivity of main-group elements like bismuth, which can mimic transition-metal behavior through oxidative addition. In their recent

• thulium nanoparticles [26] and the use of a molybdenum-centered [27] and tungsten-centered complexes have been described in the literature [28]. The work by O. S. Wenger et al. introduces a system that mimics the Z-scheme of photosynthesis, utilizing a copper(I) bis(α-diimine) complex in combination with

Three-component reactions of conjugated dienes, CH acids and formaldehyde under diffusion mixing conditions

• Dmitry E. Shybanov,
• Maxim E. Kukushkin,
• Eugene V. Babaev,
• Nikolai V. Zyk and
• Elena K. Beloglazkina

Beilstein J. Org. Chem. 2025, 21, 262–269, doi:10.3762/bjoc.21.18

• formaldehyde (generated from paraformaldehyde upon heating), an adduct of a methylidene derivative of a CH acid dienophile was detected in some cases only in reference [15] (when carrying out the reaction in a sealed tube in the presence of copper(II) acetate). However, in most reactions only the hetero-Diels

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

• Japan Synchrotron Radiation Research Institute, 1-1-1 Kouto, Sayo, Hyogo, 679-5198, Japan Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan 10.3762/bjoc.21.14 Abstract The integration of copper(I)-catalyzed three-component

• involvement of a fluorescent intermediate in the cascade synthetic process. Keywords: cascade reactions; copper-catalyzed three-component coupling; gold-mediated 6-endo hydroamination; tandem cyclizations; tetrahydroisoquinoline alkaloids; Introduction The bis-tetrahydroisoquinoline (THIQ) alkaloid family

• modular synthetic strategy involving the cascading assembly of the left THIQ segment. A concise modular synthetic process was developed to construct the substructure 14 of saframycin A (1), featuring copper(I)-catalyzed three-component coupling, and subsequent tandem 2,3-diaminobenzofuran formation

Dioxazolones as electrophilic amide sources in copper-catalyzed and -mediated transformations

• Seungmin Lee,
• Minsuk Kim,
• Hyewon Han and
• Jongwoo Son

Beilstein J. Org. Chem. 2025, 21, 200–216, doi:10.3762/bjoc.21.12

• widely used as N-acylamide sources in amidation processes of challenging substrates, typically employing precious transition metals. However, these catalytic systems often present several challenges associated with cost, toxicity, stability, and recyclability. Among the 3d transition metals, copper

• advancements in the synthetic transformations of dioxazolones, with particular examples of copper salts. Keywords: amidation; copper salts; dioxazolones; electrophilic nitrogen; N-acyl nitrene; Introduction Dioxazolones, first synthesized and reported by Beck and co-workers [1], have been employed as

• iridium (Scheme 1b) [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19]. Notably, dioxazolones have primarily been studied in directed carbon–hydrogen amidation processes, which can circumvent the need for tedious prefunctionalizations. Copper catalysts have gained recognition and attracted

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

• electrochemistry and copper catalysis for various organic transformations. Keywords: copper; electrochemistry; radical chemistry; single-electron transfer; sustainable catalysis; Introduction Transition-metal-catalyzed cross-coupling has emerged as an effective method for forming carbon–carbon (C–C) and carbon

• –heteroatom (C–X, where X = N, O, or halogens) bonds in organic synthesis. Copper was one of the first transition metals employed in cross-coupling to form C–C and C–X bonds [1][2]. In 1901, Ullmann reported the first cross-coupling reaction for the formation of biaryl compounds in the presence of

• stoichiometric quantities of a copper reagent [3]. This pioneering work, known as the “classical Ullmann reaction”, was extended by Ullmann and Goldberg to enable the C–N and C–O bond formation [4][5][6]. Subsequently, key developments in Cu-catalyzed cross-coupling reactions were achieved, including the

Nickel-catalyzed cross-coupling of 2-fluorobenzofurans with arylboronic acids via aromatic C–F bond activation

• Takeshi Fujita,
• Haruna Yabuki,
• Ryutaro Morioka,
• Kohei Fuchibe and
• Junji Ichikawa

Beilstein J. Org. Chem. 2025, 21, 146–154, doi:10.3762/bjoc.21.8

• (GlassContour) equipped with columns of activated alumina and supported-copper catalyst (Q-5) before use. 1,4-Dioxane and methanol were distilled from sodium, and stored over 4 Å molecular sieves. Unless otherwise noted, materials were obtained from commercial sources and used directly without further

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

• Venezian 21, 20133, Milano, Italy 10.3762/bjoc.21.7 Abstract This review reports the achievements in copper(II) triflate-catalyzed processes concerning the multicomponent reactions, applied to the synthesis of acyclic and cyclic compounds. In particular, for the heteropolycyclic systems mechanistic

• insights were outlined as well as cycloaddition and aza-Diels–Alder reactions were included. These strategies have gained attention due to their highly atom- and step-economy, one-step multi-bond forming, mild reaction conditions, low cost and easy handling. Keywords: cascade process; copper catalysis

• ; heteropolycycles; multicomponent reactions; one-pot reaction; Introduction Copper has gained a relevant role in organic synthesis as an alternative to precious metals due to its low toxicity, ease of handling, high catalytic activity, and cost-effectiveness [1][2]. In recent years, Cu(OTf)2 has significantly

Facile one-pot reduction of β-nitrostyrenes to phenethylamines using sodium borohydride and copper(II) chloride

• Laura D’Andrea and
• Simon Jademyr

Beilstein J. Org. Chem. 2025, 21, 39–46, doi:10.3762/bjoc.21.4

• ][18][19][20][21][22][28][29], the presence of the copper salt results in overcoming this issue and leads to isolated yields above 90% (7–9) (Scheme 2). Therefore, the NaBH4/CuCl2 system was proved to work on aromatic ester, nitro, and α,β-unsaturated nitroalkene functionalities. Our work demonstrates

• role of the CuCl2 salt is pivotal to the success of this method. Studies on the reduction of CuCl2 by NaBH4 suggest that copper(II) is promptly reduced to free Cu(0), composing up to 96% of the products. The remaining 4% consist of Cu2O and negligible amounts of other copper species [32][33

• ]. Consistently, once the chloride is added, the reduction to free Cu(0) is visually indicated by the immediate disappearance of the blue color of the copper(II) solution, and the formation of a fine suspended black powder. The latter, as metallic copper particles, acts as the actual catalyst. Time plays a

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

• was achieved in 5 steps starting from commercially available 2-bromo-4-fluoro-1-nitrobenzene (1, Scheme 1 and Scheme 2). For the preparation of the key intermediate 5 (Scheme 1), self-coupling of 1 in the presence of copper followed by reduction of the nitro group generated diamine compound 3 (89

Germanyl triazoles as a platform for CuAAC diversification and chemoselective orthogonal cross-coupling

• John M. Halford-McGuff,
• Thomas M. Richardson,
• Aidan P. McKay,
• Frederik Peschke,
• Glenn A. Burley and
• Allan J. B. Watson

Beilstein J. Org. Chem. 2024, 20, 3198–3204, doi:10.3762/bjoc.20.265

• 10.3762/bjoc.20.265 Abstract We report the synthesis of germanyl triazoles formed via a copper-catalysed azide–alkyne cycloaddition (CuAAC) of germanyl alkynes. The reaction is often high yielding, functional group tolerant, and compatible with complex molecules. The installation of the Ge moiety enables

• further diversification of the triazole products, including chemoselective transition metal-catalysed cross-coupling reactions using bifunctional boryl/germyl species. Keywords: chemoselectivity; click chemistry; copper; germanium; triazole; Introduction Since its inception, click chemistry has been

• azide precursors and the formation of a single 1,4-disubstituted triazole product, the copper-catalysed azide–alkyne cycloaddition (CuAAC) remains the archetypal click reaction (Scheme 1) [5]. The reaction has shown applicability on small and large scale, as well as under flow conditions [6], and

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

• -catalyzed aziridination of styrene (22) by chloramine-T (23, NaCl=NTs) as a source of nitrene in acetonitrile (Figure 5) [40]. No aziridine product was formed either without any source of copper or in the presence of a different copper salt, such as CuCl, CuCl2·2H2O, or CuOTf. Calix[4]pyrrole itself is

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

• -t-Bu)2. Allylic peroxidation of 3-substituted prop-1-ene-1,3-diyldibenzenes 8 was performed with TBHP as the oxidant/peroxidation agent and with Cu2O as the catalyst [42] (Scheme 6). The proposed mechanism of peroxides 9 formation does not include peroxo–copper complexes and begins with the

• formation of peroxide 9. The enantioselective peroxidation of alkenes 10 with TBHP with the formation of the optically active products 11 was carried out in good yields and low ee by the use of in situ-generated chiral bisoxazoline–copper(I) complexes (Scheme 7) [43]. Studying the oxidation of α-pinene (12

• compounds (β-diketones, β-ketoesters, and malonic esters) with TBHP via homogeneous and heterogeneous Cu(II)-catalysis were developed (Scheme 10) [45][46][47]. It was assumed that the reaction pathway includes the formation of diketonate complex A from β-dicarbonyl compound 19 and copper(II) salt, which

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

• copper catalyst afforded nearly better results for the arylated products. In 2022, Linde et al., demonstrated a conventional approach for achieving arylations of nitrogen- and oxygen nucleophiles via SNAr reaction, using o-fluorinated diaryliodonium salts 40, which enabled access to a greater range of

Investigation of a bimetallic terbium(III)/copper(II) chemosensor for the detection of aqueous hydrogen sulfide

• Parvathy Mini,
• Michael R. Grace,
• Genevieve H. Dennison and
• Kellie L. Tuck

Beilstein J. Org. Chem. 2024, 20, 2818–2826, doi:10.3762/bjoc.20.237

• /bjoc.20.237 Abstract The chemosensor properties of a bimetallic terbium(III)/copper(II) complex functionalized with a 4-(2-pyridyl)-1,2,3-triazole ligand for the detection of Cu2+ ions and, aqueous and gaseous hydrogen sulfide was investigated. The 4-(2-pyridyl)-1,2,3-triazole ligand functions both as

• of detection for aqueous hydrogen sulfide was 0.63 μM (20 ppb). No luminescent changes of the bimetallic terbium(III)/copper(II) complex were observed in the presence of gaseous hydrogen sulfide, and thus this sensor can only be used for the detection of aqueous hydrogen sulfide. Keywords

• for the detection of both gaseous and/or aqueous H2S are shown in Figure 1 [12][16][17]. These sensors all function via the copper sequestration mechanism, where upon addition of hydrogen sulfide to the quenched bimetallic species, luminescence modulation occurs. In our quest for highly selective

Synthesis and antimycotic activity of new derivatives of imidazo[1,2-a]pyrimidines

• Dmitriy Yu. Vandyshev,
• Daria A. Mangusheva,
• Khidmet S. Shikhaliev,
• Kirill A. Scherbakov,
• Oleg N. Burov,
• Alexander D. Zagrebaev,
• Tatiana N. Khmelevskaya,
• Alexey S. Trenin and
• Fedor I. Zubkov

Beilstein J. Org. Chem. 2024, 20, 2806–2817, doi:10.3762/bjoc.20.236

• ]pyrimidines thus formed did not show significant bioactivity, they found applications as additives in electrochemical copper plating processes [21][22] (Figure 2). Based on the above, the main goal of this work was to develop a convenient method for the construction of potentially pharmacophoric imidazo[1,2-a

Access to optically active tetrafluoroethylenated amines based on [1,3]-proton shift reaction

• Yuta Kabumoto,
• Eiichiro Yoshimoto,
• Bing Xiaohuan,
• Masato Morita,
• Motohiro Yasui,
• Shigeyuki Yamada and
• Tsutomu Konno

Beilstein J. Org. Chem. 2024, 20, 2776–2783, doi:10.3762/bjoc.20.233

• chlorides in the presence of a copper catalyst to afford the corresponding tetrafluoroethylenated ketones 19. The ketones were then condensed with (R)-1-phenylethylamine under the influence of TiCl4 [34][35] to prepare various optically active imines (R)-16 in high yields (Scheme 3). Based on the result of

Copper-catalyzed yne-allylic substitutions: concept and recent developments

• Shuang Yang and
• Xinqiang Fang

Beilstein J. Org. Chem. 2024, 20, 2739–2775, doi:10.3762/bjoc.20.232

• expand the scope of transition metal-catalyzed substitution reactions. Since its discovery in 2022, copper-catalyzed yne-allylic substitution has undergone rapid development and significant progress has been made using the key copper vinyl allenylidene intermediates. This review summarizes the

• developments and illustrates the influences of copper salt, ligand, and substitution pattern of the substrate on the regioselectivity and stereoselectivity. Keywords: copper-catalysis; copper vinyl allenylidene intermediate; 1,3-enyne; 1,4-enyne; yne-allylic substitution; Introduction Copper is earth

• -abundant, inexpensive, relatively stable, and low toxic. Copper-catalyzed asymmetric allylic [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22] and propargylic [23][24][25][26][27][28][29][30][31][32] substitutions are effective strategies for constructing new C–C and C

5th International Symposium on Synthesis and Catalysis (ISySyCat2023)

• Anthony J. Burke and
• Elisabete P. Carreiro

Beilstein J. Org. Chem. 2024, 20, 2704–2707, doi:10.3762/bjoc.20.227

• ) derivatives, which possess recognized pharmacological properties [12]. They used sequential reactions catalyzed by palladium and copper. The process involves an initial amination, which can be carried out via either the Buchwald–Hartwig or the Chan–Lam reaction, followed by a palladium-catalyzed

• in MeOH at room temperature with a short reaction time. Some of them were further functionalized with a 1,2,3-triazole ring via copper-catalyzed azide–alkyne cycloaddition (CuAAC) and deprotected with trifluoroacetic acid. Several hybrids were evaluated against six cancer cell lines, displaying GI50

Synthesis of fluoroalkenes and fluoroenynes via cross-coupling reactions using novel multihalogenated vinyl ethers

• Yukiko Karuo,
• Keita Hirata,
• Atsushi Tarui,
• Kazuyuki Sato,
• Kentaro Kawai and
• Masaaki Omote

Beilstein J. Org. Chem. 2024, 20, 2691–2703, doi:10.3762/bjoc.20.226

• reagents have been developed. These reagents are easily being converted into multisubstituted fluoroalkenes through cross-coupling using palladium, nickel, copper, ruthenium, and manganese catalysts [26][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41]. Hosoya and Niwa et al. published the

• ) δ −80.8 (s) and −87.6 (s) (1F, 1:1.1); EIMS (m/z): 248, 250 [M]+; HREIMS [M]+ (m/z): calcd. for C14H10ClFO, 248.0402; found, 248.0404. Sonogashira cross-coupling with multihalogenated vinyl ethers 1 To a solution of 1 (1.0 equiv), copper iodide (4 mol %), bis(triphenylphosphine)palladium dichloride

Facile preparation of fluorine-containing 2,3-epoxypropanoates and their epoxy ring-opening reactions with various nucleophiles

• Yutaro Miyashita,
• Sae Someya,
• Tomoko Kawasaki-Takasuka,
• Tomohiro Agou and
• Takashi Yamazaki

Beilstein J. Org. Chem. 2024, 20, 2421–2433, doi:10.3762/bjoc.20.206

• (17%) were employed instead of nitroacetate, while no other compound was separated from these mixtures due to their complexity (Scheme 6). Reactions of (E)-4,4,4-trifluoro-2,3-epoxybutanoate 2b with Grignard-based copper reagents Despite the previous report by the Seebach group on the intriguing

• the production of the possible olefinic product n-C8H17CH=CH2. Moreover, when the reaction mixture was quenched with D2O, incorporation of deuterium was observed to give 11a-D in a high yield which allowed us to conclude the possible presence of the C-copper species just before quenching. Our result

Synthesis, electrochemical properties, and antioxidant activity of sterically hindered catechols with 1,3,4-oxadiazole, 1,2,4-triazole, thiazole or pyridine fragments

• Daria A. Burmistrova,
• Andrey Galustyan,
• Nadezhda P. Pomortseva,
• Kristina D. Pashaeva,
• Maxim V. Arsenyev,
• Oleg P. Demidov,
• Mikhail A. Kiskin,
• Andrey I. Poddel’sky,
• Nadezhda T. Berberova and
• Ivan V. Smolyaninov

Beilstein J. Org. Chem. 2024, 20, 2378–2391, doi:10.3762/bjoc.20.202

• action of a soft oxidant a bis-(neo-cuproine) copper(II) complex. The CUPRACTEAC parameter varies in a wide range of values from 0.12 to 1.92 (Table 2). Compounds 1 and 2 containing a 1,3,4-oxadiazole ring and a sulfur atom directly bonded to the catechol ring are practically inactive in this reaction