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

• functionalized starting materials, reduces organometallic waste generation, has a broad substrate scope and a higher functional group compatibility, and features better resource- and step-economies [37][38][39][40][41][42][43][44][45][46][47]. In this context, several recent studies enabled the regioselective

Enantioselective radical chemistry: a bright future ahead

• Anna C. Renner,
• Sagar S. Thorat,
• Hariharaputhiran Subramanian and
• Mukund P. Sibi

Beilstein J. Org. Chem. 2025, 21, 2283–2296, doi:10.3762/bjoc.21.174

• enantioenriched catalysts ranging from chiral organometallic complexes to organocatalysts (small organic molecules) have been designed, synthesized, and successfully used in several organic transformations [1][2][3]. Despite these advances, catalytic methods involving radical intermediates were very rare until

• reducing ability of copper(I), substrates can be reduced to radicals and oxidize copper(I) to copper(II) in the process. Copper(II) can oxidize other organic radicals to cations by SET or reversibly react with other radicals to form copper(III) species that can undergo fundamental organometallic steps such

• substrates or organometallic complexes upon photoexcitation has enabled the synthetic community to access reactive open-shell species under very mild conditions. The ability of excited photocatalysts to induce other reagents, substrates, or other catalysts to participate in new activation modes makes them a

Enantioselective desymmetrization strategy of prochiral 1,3-diols in natural product synthesis

• Lihua Wei,
• Rui Yang,
• Zhifeng Shi and
• Zhiqiang Ma

Beilstein J. Org. Chem. 2025, 21, 1932–1963, doi:10.3762/bjoc.21.151

• enantioselective desymmetrization of prochiral 1,3-diols within complex structures can be realized using organometallic catalysts composed of copper or zinc salts and different types of chiral ligands. In general, the ability to control the stereoselectivity of the product by using the enantiomer of the ligand in

Photocatalysis and photochemistry in organic synthesis

• Timothy Noël and
• Bartholomäus Pieber

Beilstein J. Org. Chem. 2025, 21, 1645–1647, doi:10.3762/bjoc.21.128

• implement. Two decades later, photocatalysis and photochemistry remain among the most studied topics in modern organic synthesis. Nowadays, chemists can choose from a wide range of organometallic [12][13], organic [14][15], or heterogeneous photocatalysts [16][17] to trigger visible-light photoredox

Transition-state aromaticity and its relationship with reactivity in pericyclic reactions

• Israel Fernández

Beilstein J. Org. Chem. 2025, 21, 1613–1626, doi:10.3762/bjoc.21.125

• defined by Doering and Detert [6], this concept has been extended well beyond benzenoid molecules to organometallic, inorganic, and even saturated molecules. As a result, besides classical π-aromaticity, other aromaticity types such as Möebius, spherical, or excited-state aromaticity (to name a few) have

Synthesis of optically active folded cyclic dimers and trimers

• Ena Kumamoto,
• Kana Ogawa,
• Kazunori Okamoto and
• Yasuhiro Morisaki

Beilstein J. Org. Chem. 2025, 21, 1603–1612, doi:10.3762/bjoc.21.124

• substituent(s) at appropriate position(s) on the benzene rings [8]. Enantiopure planar chiral [2.2]paracyclophanes have been used as chiral auxiliaries and chiral ligands for transition metals in the fields of organic and organometallic chemistry [9][10][11][12][13][14][15][16][17][18][19][20]. In 2012

Enhancing chemical synthesis planning: automated quantum mechanics-based regioselectivity prediction for C–H activation with directing groups

• Julius Seumer,
• Nicolai Ree and
• Jan H. Jensen

Beilstein J. Org. Chem. 2025, 21, 1171–1182, doi:10.3762/bjoc.21.94

• bonds in organic chemicals. Therefore, their selective functionalization is essential for advancing the synthesis of complex molecules like pharmaceuticals, polymers, or agrochemicals [1][2][3]. Advancements in organometallic catalysis have facilitated significant progress in this area through C–H

Synthetic approach to borrelidin fragments: focus on key intermediates

• Yudhi Dwi Kurniawan,
• Zetryana Puteri Tachrim,
• Teni Ernawati,
• Faris Hermawan,
• Ima Nurasiyah and
• Muhammad Alfin Sulmantara

Beilstein J. Org. Chem. 2025, 21, 1135–1160, doi:10.3762/bjoc.21.91

• in their laboratory. The strategy primarily involved the reaction of a chiral organometallic reagent 115 with a chiral allyl electrophile 114, as depicted in Scheme 18. The resulting deoxypropionate 113 was obtained with the newly formed stereocenter controlled by the reagent directing group (RDG

• ) attached to the allyl precursor 114. Iteration of this process required ozonolysis of 113, followed by its conversion to an organometallic intermediate 116, which was then reacted with allyl 114 to yield another deoxypropionate product, 117. The synthesis began with the preparation of the precursor chiral

• undesired oxidation to the corresponding phosphane oxide. The work continued with the preparation of the chiral organometallic reagent 124. Starting from known bromide 122, which was readily accessible from Roche ester (R)-121 [52] or 1,3-diol 123 [53][54] through literature procedures, the Grignard reagent

Gold extraction at the molecular level using α- and β-cyclodextrins

• Susana Santos Braga

Beilstein J. Org. Chem. 2025, 21, 1116–1125, doi:10.3762/bjoc.21.89

• coordination with inorganic and organometallic complexes involves hydrophobic interactions and van der Waals forces (mainly with the organic parts of these guests). Several forces are at play in the formation of supramolecular assemblies with gold in the form of haloaurate ions, as detailed in the forthcoming

A convergent synthetic approach to the tetracyclic core framework of khayanolide-type limonoids

• Zhiyang Zhang,
• Jialei Hu,
• Hanfeng Ding,
• Li Zhang and
• Peirong Rao

Beilstein J. Org. Chem. 2025, 21, 926–934, doi:10.3762/bjoc.21.75

• stage was set for the construction of the target skeleton through a 1,2-addition (Scheme 4). Preliminary trials to generate organometallic species via Li/I exchange under various conditions (n-BuLi, t-BuLi, or t-BuLi in combination with CeCl3 or MgBr2) led to rapid decomposition, likely due to inherent

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

• , 3663 North Zhongshan Road, Shanghai 200062, PR China School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007, PR China State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road

Development and mechanistic studies of calcium–BINOL phosphate-catalyzed hydrocyanation of hydrazones

• Carola Tortora,
• Christian A. Fischer,
• Sascha Kohlbauer,
• Alexandru Zamfir,
• Gerd M. Ballmann,
• Jürgen Pahl,
• Sjoerd Harder and
• Svetlana B. Tsogoeva

Beilstein J. Org. Chem. 2025, 21, 755–765, doi:10.3762/bjoc.21.59

• Erlangen-Nürnberg, Nikolaus-Fiebiger Strasse 10, 91058 Erlangen, Germany Department of Chemistry and Pharmacy, Chair of Inorganic and Organometallic Chemistry, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstrasse 1, 91058 Erlangen, Germany 10.3762/bjoc.21.59 Abstract Asymmetric

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

• scope and efficiency of these reactions. A notable advancement came from Knochel's introduction of dialkylzinc reagents in 1999, which substantially broadened the range of applicable organometallic compounds [23]. Subsequent significant progress was achieved independently by Feringa and Alexakis through

• their exploration of phosphoramidite ligands with various organometallic nucleophiles [24][25]. The field was further advanced by the research group of Hoveyda, who made substantial contributions by introducing bidentate N-heterocyclic carbene (NHC)-based chiral ligands, achieving high selectivity with

• into a powerful and versatile tool in asymmetric synthesis, capable of employing a wide array of organometallic reagents that furnish the desired compounds with high efficiency and selectivity. The regioselective asymmetric construction of stereogenic carbon centers from prochiral allylic substrates

Sequential two-step, one-pot microwave-assisted Urech synthesis of 5-monosubstituted hydantoins from L-amino acids in water

• Wei-Jin Chang,
• Sook Yee Liew,
• Thomas Kurz and
• Siow-Ping Tan

Beilstein J. Org. Chem. 2025, 21, 596–600, doi:10.3762/bjoc.21.46

• ]. Furthermore, several methods for hydantoin synthesis have been reported. The modified Bucherer–Bergs reaction using nitriles or methyleneaziridines with organometallic reagents gave moderate yields of 40–77% and 48–75%, respectively [7][8]. Amino acids remain key building blocks, with approaches involving

Organocatalytic kinetic resolution of 1,5-dicarbonyl compounds through a retro-Michael reaction

• James Guevara-Pulido,
• Fernando González-Pérez,
• José M. Andrés and
• Rafael Pedrosa

Beilstein J. Org. Chem. 2025, 21, 473–482, doi:10.3762/bjoc.21.34

• organometallic catalysis [15], enzymatic catalysis [16], aminocatalysis [17][18][19], and hydrogen-bonding catalysis [20][21][22]. The Michael addition reaction is a versatile synthetic methodology that allows the formation of new carbon–carbon and carbon–heteroatom bonds through the coupling of electron-poor

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

• , exceptional thermal and chemical stability, and robust synthetic versatility [16][17] – make carborane derivatives essential components in various fields. These include pharmaceuticals [18][19][20][21][22], boron neutron capture therapy (BNCT) [23][24][25][26], organometallic ligands [27], and functional

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

• applied in various fields, including organometallic catalysis, dye-sensitized solar cells, sensing, artificial olfactory systems, photodynamic therapy (PDT), anticancer drugs, biochemical probes, and electrochemical devices. Relevant examples of these two pyrrolic macrocycles as metal-free organocatalysts

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

• or without the use of transition metals [44]. Thus, they address both the financial and environmental challenges associated with organic synthesis by acting as environmentally benign substitutes for costly organometallic catalysts and heavy-metal-based oxidants. Diaryl iodide salts consist of two

• 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

Multicomponent synthesis of α-branched amines using organozinc reagents generated from alkyl bromides

• Baptiste Leroux,
• Alexis Beaufils,
• Federico Banchini,
• Olivier Jackowski,
• Alejandro Perez-Luna,
• Fabrice Chemla,
• Marc Presset and
• Erwan Le Gall

Beilstein J. Org. Chem. 2024, 20, 2834–2839, doi:10.3762/bjoc.20.239

• ]. Since its discovery in 1912, the reaction has benefitted from regular improvements over the years and recent developments, such as the use of organometallic species as nucleophiles in the so-called “organometallic Mannich reaction”, which have helped to expand the boundaries of the original process [4

• ]. In this context, while significant contributions have highlighted the reliable use of diverse organometallic species in the three-component coupling, most examples of sp3-hybridized compounds have remained restricted to allyl [5] or benzyl [5][6] organometallic reagents. Conversely, examples of

• organometallic Mannich couplings involving nonstabilized organometallics are uncommon and mostly limited to dialkylzinc reagents, likely due to their commercial availability, their significant reactivity, and their functional-group tolerance [7][8][9][10]. However, the molecular diversity accessible with these

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

• organometallic species [16][17][18][19]. At least in part, its high reactivity was considered to be due to the significantly lower-lying LUMO energy level by the attachment of electron-withdrawing trifluoromethyl (CF3) and ethoxycarbonyl groups [20]. As we previously pointed out [10][21], the effective

• preparation of 2a. Moreover, the fact that only very limited examples are known for their synthetic application except for the synthesis of 4,4,4-trifluorothreonine [29][33], stereoselective ring opening with organometallic species [29], and so on [32] also stimulated our interest. In this article, we would

• reactivity of the CF3-containing ethyl 2,3-epoxybutanoate 2a towards a variety of organometallic species [27][28][29], because relatively readily accessible Grignard-based cuprates were not involved, their applicability to 2b as the representative partner was investigated here (Table 5). The 1:2 ratio of CuI

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

• , Russia G.A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Tropinin str. 49, 603137, Nizhny Novgorod, Russia North-Caucasus Federal University, Pushkin str. 1, 355017, Stavropol, Russia Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences

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

• as a key methodology in the synthesis of alkaloids and natural products with 4-, 5- and 6-membered cyclic amine motifs. Initially reliant on stoichiometric reagents, synthetic chemists predominantly used N-substituted chiral imines, organometallic chiral reagents and achiral reagents with an

Multicomponent syntheses of pyrazoles via (3 + 2)-cyclocondensation and (3 + 2)-cycloaddition key steps

• Ignaz Betcke,
• Alissa C. Götzinger,
• Maryna M. Kornet and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2024, 20, 2024–2077, doi:10.3762/bjoc.20.178

Carbonylative synthesis and functionalization of indoles

• Alex De Salvo,
• Raffaella Mancuso and
• Xiao-Feng Wu

Beilstein J. Org. Chem. 2024, 20, 973–1000, doi:10.3762/bjoc.20.87

• recent achievements on the synthesis and functionalization of indole derivatives via carbonylative approaches. Keywords: carbonylation; functionalization; indole; metal catalyst; organometallic chemistry; Introduction Indole is a heterocyclic compound consisting of a benzene ring fused with a pyrrole

Skeletal rearrangement of 6,8-dioxabicyclo[3.2.1]octan-4-ols promoted by thionyl chloride or Appel conditions

• Martyn Jevric,
• Julian Klepp,
• Johannes Puschnig,
• Oscar Lamb,
• Christopher J. Sumby and
• Ben W. Greatrex

Beilstein J. Org. Chem. 2024, 20, 823–829, doi:10.3762/bjoc.20.74

• the glycosidic bond using an organometallic purine or pyrimidine derivative and an electrophilic furanose derivative [23][25]. This process can result in anomeric mixtures, so 5 has potential applications in targeted synthesis, as the configuration of the pseudo-anomeric centre matches the common