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

• used to achieve higher yields [27]. Even in the absence of a transition-metal-based photosensitizer, a recent study showed that perfluoroalkylation using perfluoroalkyl iodides (RFI) could be carried out by activation of the RF–I bonds by formation of electron donor–electron acceptor complexes with an

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

• enzyme dynamics. The wider history of supramolecular and cavity catalysis [3][13][15][16][17][18][19][21][48][49], and catalysis using confined transition-metal catalysts [50][51][52], dendrimers [53] or synzymes [54], micelles [55] or vesicles [56], catalytic antibodies [57][58][59] or molecularly

• host catalysis – (i) using the host as a “protecting group” to direct reactivity external to the host [187][346], and (ii) confinement of a transition-metal catalyst to take advantage of the restricted environment of the host [51][52] – neither of which resembles the enzyme-like possibility of a true

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

• . 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

• explores how this bismuth(I) complex undergoes oxidative addition with a variety of aryl electrophiles, including diazonium salts, iodonium salts, and challenging aryl iodides and aryl thianthrenium salts, typically requiring transition-metal catalysts (Figure 3). The reactivity of the N,C,N-bismuthinidene

• transition-metal catalysis. As the use of osmium catalysts has already demonstrated scalability in industrial applications [22], the introduction of bismuthinidene complexes presents another step forward in expanding the photoredox catalysis toolkit, potentially paving the way for more sustainable and

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

• electrophiles in various nucleophilic transformations due to their susceptibility to rapid decomposition into the corresponding isocyanates (Scheme 1a) [2][3]. They have attracted increasing interest as electrophilic amide sources in amidation using transition-metal catalysts such as ruthenium, rhodium, and

• potential bioactivity [70][71][72][73]. Despite the development of synthetic approaches for six-membered lactams, including transition-metal-catalyzed transformations, several limitations remain, particularly with regard to regioselectivity and asymmetric C–N bond formation, which are still limited. In 2023

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

• chemistry. Combining electrochemistry with transition-metal catalysis is a promising and rapidly growing methodology for effectively forming challenging C–C and C–heteroatom bonds in complex molecules in a sustainable manner. In this review, we summarize the recent advances in the combination of

• 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

• remains a significant challenge owing to the high energy barrier required for oxidative addition and facile β-hydride elimination [12]. The development of radical approaches facilitated by transition-metal catalysis has provided a promising solution to overcome the limitations of conventional coupling

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

• transition-metal catalysts provides synthetic tools even more advantageously. Copper has also become very interesting in this field, mainly in processes aimed at synthesizing heterocyclic compounds. Among the various catalysts, Cu(OTf)2 stands out in heterocyclic synthesis and ring transformations due to its

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

• purities, solid yields and very good diastereomeric ratios. The hydroxy group present in products 156 and 158 could be transformed to provide axially chiral phosphines that could be utilized as chiral ligands in transition-metal-catalyzed reactions. Testing both substrates 156 and 158 for conformational

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

• limited, since a NaBH4/transition metal salt system is mostly used to reduce nitroarenes [23][24][25][26]. One of the reported methods takes advantage of titanium(IV) isopropoxide as a catalyst to prepare varied β-phenethylamine analogues. Despite its simplicity, the reaction time is quite prolonged (from

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

• commercial perfluoroarene chemical blocks and reagents, involving catalyzed C–F-bond activation and cross-coupling reactions, usually requiring precious transition-metal catalysts and tedious synthetic routes [28][29][30][31][32][33][34]. Therefore, low-cost and facile synthetic strategies are desired to

Intramolecular C–H arylation of pyridine derivatives with a palladium catalyst for the synthesis of multiply fused heteroaromatic compounds

• Yuki Nakanishi,
• Shoichi Sugita,
• Kentaro Okano and
• Atsunori Mori

Beilstein J. Org. Chem. 2024, 20, 3256–3262, doi:10.3762/bjoc.20.269

• ; phosphine ligand; pyridine amides; Introduction Transition-metal-catalyzed synthetic reactions have recently attracted much attention in synthetic organic chemistry [1][2]. C–H Arylation reactions catalyzed by a transition metal are of particular interest because these reactions involve rather superior

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

• 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

• proven useful in various Cu- and Pd-catalysed C–X-bond-forming strategies [43][44][45][46][47][48][49][50][51], including widespread use across several CuAAC methodologies [52][53][54]. Germanium-based functional groups have recently emerged as highly useful components for transition-metal-catalysed

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

• macrocycles as electrocatalysts Development of efficient renewable technologies is a driving force in the efforts to achieve sustainability with the same or even increasing demands for energy worldwide. In this context, transition-metal complexes of tetraazamacrocycles (N4-macrocycle) such as porphyrins

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

• substitution/addition reactions became the standard for end-capping reactions, although a transition metal–catalyzed cross-coupling reaction has also been used to synthesize CD-based rotaxane. Typically, water-soluble components are prepared, after which the Suzuki coupling reaction in water is used to

• such stimuli. When the rotaxane motif contains cyclophane or a crown ether, stimuli induced by a transition metal or an electrostatic interaction have been widely used. These interactions are easily controlled, and they induce relatively strong coordination interactions among the components, making

• them suitable media for regulating the rotaxane structure. Concurrently, for CD-based rotaxane systems, employing a transition metal or inducing electrostatic interactions encounters more limitations owing to the synthetic shortcoming of integrating high-polar moieties in their dumbbell framework that

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

• -scission [31][32], which can lead to side reactions. Some aspects of the rich metal–peroxide redox chemistry have been discussed in previous reviews [33]. Specifically, the radical functionalization of C–C bonds accessed through the transition metal-mediated reduction of organic peroxides has been covered

• with radical B to form product 73. The mechanism of the transition metal-catalyzed oxidation of amines with TBHP was studied in detail in the work of Doyle and Ratnikov [71]. The scope of the amines 74 that can be functionalized by the tert-butylperoxy fragment was significantly broadened by using a

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

• -arylations utilizing diaryliodonium salts, marked by significant contributions, notably from research teams led by Sanford [53] and Gaunt [54]. The synthesis of carbon–carbon bonds through metal-free approaches serves as a valuable complement to transition-metal-catalyzed couplings. This is particularly

• salt, subsequently leading to decarboxylative C–C coupling. Notably, this method achieves the incorporation of two fluorine atoms in the benzyl position without resorting to hazardous fluorination reagents, transition-metal catalysts, or organometallic compounds. The utility of this reaction is

• efficiency and effectiveness as a synthetic approach. Furthermore, a transition-metal-free arylation of quinoxalines 17 and quinoxalinones 19 via aryl radicals was discussed by Li and co-workers in 2022. In this report the aryl radicals were generated by planetary ball milling of diaryliodonium salts 16 at a

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

• various transformations [54][55][56][57][58][59][60][61][62][63][64]. In consequence, a large number of transition-metal-catalyzed or radical-mediated processes for C–H functionalization of aldehyde hydrazones has flourished over the years. An ideal scenario for a direct and sustainable synthetic route

C–C Coupling in sterically demanding porphyrin environments

• Liam Cribbin,
• Brendan Twamley,
• Nicolae Buga,
• John E. O’ Brien,
• Raphael Bühler,
• Roland A. Fischer and
• Mathias O. Senge

Beilstein J. Org. Chem. 2024, 20, 2784–2798, doi:10.3762/bjoc.20.234

• further substitution directly on the meso- or a meso-phenyl ortho/meta/para positions of a porphyrin, is the introduction of C–C bond forming chemistry. This is typically achieved using palladium and/or another transition-metal catalyst [20]. Sonagashira [21], Suzuki–Miyaura [22], Heck [23], Stille [24

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

• rearomatization In 2023, Lin and He et al. [72] achieved the challenging dearomatization of heteroarenes through d-orbital electron of the transition-metal center and thus completed the asymmetric substitutions with remote stereoselective control induced by alkynylcopper. A newly electron-rich ligand was

• propargylic substitution and allylic substitution, but represents a new type of reaction mode, and greatly expands the scope of transition metal-catalyzed substitution reactions. Currently, yne-allylic substitutions affording 1,3- or 1,4-enynes, remote substitutions through dearomatization-rearomatization

Computational design for enantioselective CO₂ capture: asymmetric frustrated Lewis pairs in epoxide transformations

• Maxime Ferrer,
• Iñigo Iribarren,
• Tim Renningholtz,
• Ibon Alkorta and
• Cristina Trujillo

Beilstein J. Org. Chem. 2024, 20, 2668–2681, doi:10.3762/bjoc.20.224

• studies, but the stereochemical aspects of this reaction, particularly through the use of FLP catalysts, have been largely overlooked, despite the prevalence of racemic epoxide solutions. Only one study has addressed the asymmetric insertion of CO2 into propylene oxide (PO) using a transition-metal

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

• , Trombay, Mumbai-400085, India Homi Bhabha National Institute, Anushaktinagar, Mumbai, PIN-400094, India 10.3762/bjoc.20.223 Abstract A transition-metal-free decarbonylation–oxidation protocol for the conversion of 3-arylbenzofuran-2(3H)-ones to 2-hydroxybenzophenones under mild conditions has been

• abilities has been verified by mathematical calculations. Keywords: decarbonylation–oxidation; hydroperoxide; 2-hydroxybenzophenone; transition-metal-free; UV-protection; Introduction Benzophenone compounds are ubiquitous in nature, and show biological activities such as anti-inflammatory, antiviral, and

• environmental hazards, and this can only be circumvented using a transition-metal-free synthesis protocol. Although eco-friendly methods for the synthesis of 2-hydroxybenzophenones have been reported via a cycloaromatization of α-alkenoyl ketene dithioacetals and nitroethane in water [15], an alternate and more

Transition-metal-free synthesis of arylboronates via thermal generation of aryl radicals from triarylbismuthines in air

• Yuki Yamamoto,
• Yuki Konakazawa,
• Kohsuke Fujiwara and
• Akiya Ogawa

Beilstein J. Org. Chem. 2024, 20, 2577–2584, doi:10.3762/bjoc.20.216

• under transition-metal-free and open-air conditions. Conventional methods required photoirradiation or electrolysis to generate aryl radicals from triarylbismuthines. In this study, it was found that simply heating the solution of triarylbismuthines in benzotrifluoride (BTF) in air successfully led to

• the generation of aryl radicals, and the subsequent reaction with bis(pinacolato)diboron afforded a variety of arylboronates in moderate to good yields. Keywords: arylboronates; bis(pinacolato)diboron; radical reactions; transition-metal-free synthesis; triarylbismuthines; Introduction Arylboronates

• variety of transition-metal-catalyzed reactions and photoredox reactions using arylboronates as aryl sources have been energetically investigated for the construction of carbon–carbon or carbon–heteroatom bonds [12][13][14][15]. The preparation of arylboronates often requires pre-functionalized substrates

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

• [3]. Transition-metal-catalyzed LSF strategies have been well-established over the past decades. More recently, with the vigorous development of photochemistry and electrochemistry, numerous innovative reports on LSF using photo-, electro-, and photoelectrochemistry have emerged. These areas have

• was demonstrated by the LSF of primary natural and pharmaceutical amines carrying potential competing nucleophiles, such as tryptamine and primaquine (Scheme 16). In the context of electrochemical difunctionalizations the Lei group published a transition-metal-free electrochemical difunctionalization

• group. Based on extensive mechanistic studies, they proposed the formation of a formal Ni(IV) complex during the process. Remarkably, nickel proved to be uniquely effective for this protocol, as other transition-metal catalysts based on Cu, Co, Pd, Ir, Ru, and Rh did not catalyze the reaction (Scheme 36

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

• equimolar chiral controller. However, recent years have witnessed the rise of asymmetric transition-metal catalysts and, importantly, organocatalytic allylation, reshaping the landscape of modern synthetic chemistry. This review explores the latest developments in the asymmetric allylation of imines

Hydrogen-bond activation enables aziridination of unactivated olefins with simple iminoiodinanes

• Phong Thai,
• Lauv Patel,
• Diyasha Manna and
• David C. Powers

Beilstein J. Org. Chem. 2024, 20, 2305–2312, doi:10.3762/bjoc.20.197

• general, transition metal catalysts are required to effect efficient NGT to unactivated olefins because iminoiodinanes are insufficiently electrophilic to engage in direct aziridination chemistry. Here, we demonstrate that 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) activates N-arylsulfonamide-derived

• ]. Iminoiodinanes (ArI=NR) are a subclass of hypervalent iodine reagents that function as nitrene equivalents in synthesis [5][6]. The direct reaction of iminoiodinanes with olefins, which could be envisioned to give rise to aziridines directly, is typically not observed and thus families of transition metal

• Discussion Treatment of cyclohexene (1a) with a stoichiometric amount of simple iminoiodinane such as PhINTs (2a) in CH2Cl2 resulted in <10% conversion to the corresponding N-sulfonylaziridine 3a, which is consistent with the previously reported need for transition metal catalysts to promote nitrene transfer

Catalysing (organo-)catalysis: Trends in the application of machine learning to enantioselective organocatalysis

• Stefan P. Schmid,
• Leon Schlosser,
• Frank Glorius and
• Kjell Jorner

Beilstein J. Org. Chem. 2024, 20, 2280–2304, doi:10.3762/bjoc.20.196

• Research (NCCR) Catalysis, ETH Zurich, Zurich CH-8093, Switzerland 10.3762/bjoc.20.196 Abstract Organocatalysis has established itself as a third pillar of homogeneous catalysis, besides transition metal catalysis and biocatalysis, as its use for enantioselective reactions has gathered significant

• . Keywords: catalyst design; machine learning; modelling; organocatalysis; selectivity prediction; Introduction Since the beginning of the 21st century, organocatalysts [1] have established themselves as a third group of homogeneous catalysts, next to biocatalysts [2] (enzymes) and transition metal-based

• pitfall regarding computational data is its accuracy with respect to the ground truth, in particular for multiple factors relevant throughout catalysis, such as non-covalent interactions (NCIs) for organocatalysis or spin properties for transition metal catalysis [35][36]. While most quantities can in