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

SOMOphilic alkyne vs radical-polar crossover approaches: The full story of the azido-alkynylation of alkenes

• Julien Borrel and
• Jerome Waser

Beilstein J. Org. Chem. 2024, 20, 701–713, doi:10.3762/bjoc.20.64

• elimination of the organometallic intermediate would lead to the desired product (Scheme 1B, reaction 1). Unfortunately, this approach will not be compatible in the case of azidation since the copper, azides and alkynes present in the mixture are expected to undergo alkyne–azide cycloaddition reactions [28

A laterally-fused N-heterocyclic carbene framework from polysubstituted aminoimidazo[5,1-b]oxazol-6-ium salts

• Andrew D. Gillie,
• Matthew G. Wakeling,
• Bethan L. Greene,
• Louise Male and
• Paul W. Davies

Beilstein J. Org. Chem. 2024, 20, 621–627, doi:10.3762/bjoc.20.54

• ; imidazolium; NHC; Introduction Imidazolium-derived nucleophilic heterocyclic carbenes (NHCs) have had a sustained impact across the fields of organometallic and main group chemistry, transition-metal catalysis, materials synthesis and organocatalysis [1]. Laterally annellated polycyclic NHCs offer a useful

Ligand effects, solvent cooperation, and large kinetic solvent deuterium isotope effects in gold(I)-catalyzed intramolecular alkene hydroamination

• Ruichen Lan,
• Brock Yager,
• Yoonsun Jee,
• Cynthia S. Day and
• Amanda C. Jones

Beilstein J. Org. Chem. 2024, 20, 479–496, doi:10.3762/bjoc.20.43

• hydroamination (1b) a KIE of 2.4 is estimated based on their statement of percent conversions in MeOH (61%) compared to MeOH-d4 (25%) after 20 hours at 50 °C [7]. Large isotope effects (>7) have been seen in a number of organometallic reactions [75] and tunneling need not be invoked if proton transfer involves

(E,Z)-1,1,1,4,4,4-Hexafluorobut-2-enes: hydrofluoroolefins halogenation/dehydrohalogenation cascade to reach new fluorinated allene

• Nataliia V. Kirij,
• Andrey A. Filatov,
• Yurii L. Yagupolskii,
• Sheng Peng and
• Lee Sprague

Beilstein J. Org. Chem. 2024, 20, 452–459, doi:10.3762/bjoc.20.40

• ) and butyllithium (BuLi), as well as the reactions of the resulting organometallic compounds. 1.2 Equivalents of a solution of iPrMgCl in THF were added to bromoolefin 3a in Et2O or THF at −78 °C and then after 1 h at the same temperature 1 equivalent of 4-fluorobenzaldehyde (9) was added. After

Mechanisms for radical reactions initiating from N-hydroxyphthalimide esters

• Carlos R. Azpilcueta-Nicolas and
• Jean-Philip Lumb

Beilstein J. Org. Chem. 2024, 20, 346–378, doi:10.3762/bjoc.20.35

• decarboxylative cross-coupling (DCC) of NHPI esters with organometallic reagents, resembling classic Kumada, Negishi, and Suzuki couplings, has been enabled by nickel (Ni), cobalt (Co), iron (Fe), and copper (Cu) catalysts [84][85][86][87][88][89][90][91] (Scheme 23A). The typical mechanism begins by

• transmetallation of the organometallic coupling partner 120 to the TM catalyst (Scheme 23B). The resulting organometallic intermediate 121 can act as a reducing agent, transferring an electron to RAE 10 to form radical anion 11 and the corresponding oxidized metal complex 122. Following fragmentation, the ensuing

Catalytic multi-step domino and one-pot reactions

• Svetlana B. Tsogoeva

Beilstein J. Org. Chem. 2024, 20, 254–256, doi:10.3762/bjoc.20.25

• stereocenters [7]. In the Review paper by Kisszékelyi and Šebesta, the diverse variety of chiral metal enolates obtained by asymmetric conjugate additions of organometallic reagents and the possibilities to engage metal enolates in tandem reactions with new electrophiles are presented [8]. A Perspective from X

Aldiminium and 1,2,3-triazolium dithiocarboxylate zwitterions derived from cyclic (alkyl)(amino) and mesoionic carbenes

• Nedra Touj,
• François Mazars,
• Guillermo Zaragoza and
• Lionel Delaude

Beilstein J. Org. Chem. 2023, 19, 1947–1956, doi:10.3762/bjoc.19.145

• just three decades (Figure 1) [2]. In particular, cyclic diaminocarbenes based on the imidazoline, benzimidazole, or imidazole ring system (A–C) have led to a myriad of applications in organometallic chemistry, homogeneous catalysis, and materials science, to name just a few [3][4][5]. Due to their

Active-metal template clipping synthesis of novel [2]rotaxanes

• Cătălin C. Anghel,
• Teodor A. Cucuiet,
• Niculina D. Hădade and
• Ion Grosu

Beilstein J. Org. Chem. 2023, 19, 1776–1784, doi:10.3762/bjoc.19.130

• Catalin C. Anghel Teodor A. Cucuiet Niculina D. Hadade Ion Grosu Babeș-Bolyai University, Faculty of Chemistry and Chemical Engineering, Supramolecular Organic and Organometallic Chemistry Centre, 11 Arany Janos Str., RO-400028-Cluj-Napoca, Romania University of Bucharest, Faculty of Chemistry

Trifluoromethylated hydrazones and acylhydrazones as potent nitrogen-containing fluorinated building blocks

• Zhang Dongxu

Beilstein J. Org. Chem. 2023, 19, 1741–1754, doi:10.3762/bjoc.19.127

• =N motif within hydrazones gives them both electrophilic and nucleophilic character. In 2005, Brigaud et al. developed a highly stereoselective method for the synthesis of α-trifluoromethylamines with organometallic reagents to extend the asymmetric methodologies of trifluoroacetaldehyde hydrazones

• building blocks [91] (Scheme 14). Inspired by previous accounts and this work [92][93], Hu et al. explored 1,2- nucleophilic addition reactions of trifluoromethylated acylhydrazones with organometallic reagents for the synthesis of trifluorinated homoallylic acylhydrazines [94][95][96][97][98

• Brønsted acid-assisted Lewis base catalysis. Synthesis of CF3-pyrazoles and CF3-1,6-dihydropyridazines. Asymmetric reactions of trifluoromethylimines with organometallic reagents. Mannich-type reaction of trifluoroacetaldehyde hydrazones. Synthesis of trifluoromethylated hydrazonoyl halides. Early work of