The trans-influence in gold chemistry from a catalytic perspective

• Manfred Bochmann

Beilstein J. Org. Chem. 2026, 22, 838–856, doi:10.3762/bjoc.22.66

• . This effect is probably more dominant in gold chemistry than in most other transition-metal complexes; it can on occasions appear even more important than the formal oxidation state and d-electron count. Tilset and co-workers have recently summarised the importance of the trans-influence in C^N

Unsymmetrical sulfoxides with sterically hindered catechol fragment: synthesis, structure, electrochemical properties, and antiradical activity

• Daria A. Burmistrova,
• Vasiliy A. Fokin,
• Oleg P. Demidov,
• Mikhail A. Kiskin,
• Maxim V. Arsenyev,
• Andrey I. Poddel’sky,
• Nadezhda T. Berberova and
• Ivan V. Smolyaninov

Beilstein J. Org. Chem. 2026, 22, 828–837, doi:10.3762/bjoc.22.65

• soft sulfoxide group within a single molecule also provides a basis for the preparation of metal complexes with unusual properties. The aim of the present work is to synthesize new unsymmetrical sulfoxides bearing hydrocarbon fragments derived from catechol thioethers, to study their structure and

• antioxidants, stimuli-responsive materials, and functional ligands for metal complexes with tailored electronic properties. Molecular structures of 1a (a), 4a (b), 5a (c), 6a (d), 7a (e) (solvent molecules and fragment disordering are omitted; for 4a and 5a, only one independent molecule is shown). CV curves

Knoevenagel condensation of 4,5- and 1,8-diazafluorenes

• Darya S. Cheshkina,
• Christina S. Becker,
• Alina A. Sonina and
• Maxim S. Kazantsev

Beilstein J. Org. Chem. 2026, 22, 803–812, doi:10.3762/bjoc.22.62

• be applied as antitumor agents [1][2][3], emitters and sensors [4][5]. They have also been extensively used as ligands yielding a wide library of transition-metal complexes [6][7][8], catalysts [9][10], light-driven molecular motors [11][12], nonlinear optical chromophores [13], and electrochromic

Synthesis of heterocycles based on azomethine ylides from α-amino acids (or amines) and carbonyl compounds

• Ekaterina V. Berezhnaya,
• Alexander I. Ponyaev,
• Vitali M. Boitsov and
• Alexander V. Stepakov

Beilstein J. Org. Chem. 2026, 22, 705–741, doi:10.3762/bjoc.22.55

• chiral metal complexes of Ag(I), Cu(I/II), Zn(II), Ni(II) with ligands of the Segphos, Fesulfos, or Biphamphos type [12][13][14][15]. Such catalytic systems control the enantioselectivity of cycloaddition and allow the preparation of enantioenriched pyrrolidines containing several stereocenters in high

• diastereoselectivity in the catalytic (3 + 2) cycloaddition between iminoethers and electrophilic alkenes occurring using chiral metal complexes based on copper(I) and silver(I) salts and ligands (S)-DM-Segphos (L12) or (S)-DTBM-Segphos (L11) (Scheme 12). The reactions involved various dipolarophiles such as acrylates

• key factor in controlling enantioselectivity. Replacing the bicyclic heteroarene with a monocyclic one reduces the steric burden and inverse enantioselectivity is observed [31]. Today, the reactions of [6 + 3] cycloaddition of imines to fulvenes, catalyzed by chiral metal complexes, are well known

Photoorganocatalytic trifluoromethylation of (het)arenes in green conditions

• Egor N. Boronin,
• Svetlana E. Kaurkina,
• Milena M. Svetlakova,
• Anton S. Bolshakov,
• Maxim V. Arsenyev,
• Vasilii F. Otvagin,
• Alexey Yu. Fedorov,
• Timothy Noël and
• Alexander V. Nyuchev

Beilstein J. Org. Chem. 2026, 22, 662–671, doi:10.3762/bjoc.22.50

• -based complexes to other transition metals and organic photocatalysts, as well as diverse CF3 sources. The major limitations of these methodologies include the high cost of catalysts and trifluoromethylating reagents, along with the use of toxic species such as transition-metal complexes and hazardous

Kinetic resolution of racemic planar-chiral vinylcymantrenes by molybdenum-catalyzed asymmetric metathesis dimerization

• Haruna Imazu,
• Hitoshi Izu,
• Yasuhiro Ohki and
• Masamichi Ogasawara

Beilstein J. Org. Chem. 2026, 22, 568–574, doi:10.3762/bjoc.22.42

• metathesis chemistry, and various chiral metal-alkylidene catalysts have been prepared over the past two decades [6][7][8][9]. Since 2002, our group and others have been interested in utilizing the olefin metathesis reaction for the modulation of various transition-metal complexes [10][11][12][13] thanks to

• the excellent tolerance of the Mo-/Ru-metathesis catalysts toward the organometallic substrates. The olefin metathesis protocols could be extended to the asymmetric synthesis of diverse planar-chiral transition metal complexes either by the kinetic resolution of the racemic substrates [14][15][16] or

• by the desymmetrization of the Cs-symmetric substrates [17][18][19] by the use of an appropriate chiral catalyst (see the drawing in Table 1 for the structures of the representative chiral molybdenum precatalysts used in this study) [20][21][22][23]. Planar-chiral transition-metal complexes have been

Design and synthesis of an axially chiral platinum(II) complex and its CPL properties in PMMA matrix

• Daiki Tauchi,
• Sota Ogura,
• Misa Sakura,
• Kazunori Tsubaki and
• Masashi Hasegawa

Beilstein J. Org. Chem. 2026, 22, 143–150, doi:10.3762/bjoc.22.7

• Luminescent materials based on metal complexes have been extensively studied due to their high phosphorescence efficiency, making them promising candidates for applications in organic light-emitting diodes (OLEDs) [1][2][3][4][5], sensors [6][7][8][9], and bioimaging materials [10][11]. Among these materials

• also from the perspective of fundamental chemistry. In recent years, the design and synthesis of luminescent pincer-type platinum(II) metal complexes incorporating chirality, as well as the study of their physicochemical properties, have gained significant interest [18][19][20][21][22]. Such efforts

• −3, highlighting the role of restricted molecular motion in enhancing chiroptical properties. These findings underscore the potential of axial chirality as a design principle for developing chiral phosphorescent materials and open avenues for further exploration of chiral metal complexes in

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

• different transition-metal complexes have been employed in metalloradical catalysis, including porphyrin complexes of cobalt(II) [55][56] and iron(III) [57][58]. Both cobalt in oxidation state +2 and iron in oxidation state +3 can be viewed as persistent metalloradicals. Zhang and co-workers reported a

• , organocatalysts, transition-metal complexes, and enzymes. In many cases, low catalyst loadings have been achieved, especially in transition-metal catalyzed, photoredox, and biocatalytic methods. Photoredox catalysis has had a tremendous impact on the field of organic radical chemistry. In many modern radical

Photochemical reduction of acylimidazolium salts

• Michael Jakob,
• Nick Bechler,
• Hassan Abdelwahab,
• Fabian Weber,
• Janos Wasternack,
• Leonardo Kleebauer,
• Jan P. Götze and
• Matthew N. Hopkinson

Beilstein J. Org. Chem. 2025, 21, 1973–1983, doi:10.3762/bjoc.21.153

• transition-metal complexes such as the Grubbs’ second-generation metathesis catalyst, NHCs are now also well-established as organocatalysts. With the first application pre-dating the unambiguous characterization of a free NHC by nearly 50 years, NHCs can facilitate numerous synthetically attractive

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

• been developed, employing enzymes, metal complexes, or organocatalysts to convert prochiral or meso precursors into chiral motifs. Different from other strategies constructing chiral centers by formation of a new chemical bond at the central carbon, enantioselective desymmetrization is achieved through

Stereoselective electrochemical intramolecular imino-pinacol reaction: a straightforward entry to enantiopure piperazines

• Margherita Gazzotti,
• Fabrizio Medici,
• Valerio Chiroli,
• Laura Raimondi,
• Sergio Rossi and
• Maurizio Benaglia

Beilstein J. Org. Chem. 2025, 21, 1897–1908, doi:10.3762/bjoc.21.147

• products, agrochemicals, and pharmacologically active compounds. Enantiomerically pure 1,2-diamines and their derivatives are also increasingly used in stereoselective synthesis, particularly as chiral auxiliaries or as ligands for metal complexes in asymmetric catalysis [1]. Metal-based reductants

• photochemical and electrochemical methods, have been explored. Over the past two decades a variety of light-promoted imino-pinacol coupling reactions have been developed, involving the use of catalytic transition-metal complexes [35][36], organic dyes [37][38][39], and polyaromatic compounds [40][41] as

Fe-catalyzed efficient synthesis of 2,4- and 4-substituted quinolines via C(sp²)–C(sp²) bond scission of styrenes

• Prafull A. Jagtap,
• Manish M. Petkar,
• Vaishnavi R. Sawant and
• Bhalchandra M. Bhanage

Beilstein J. Org. Chem. 2025, 21, 1799–1807, doi:10.3762/bjoc.21.142

• probes for sensing and bioimaging applications (Figure 1) [16][17]. Quinoline-derived metal complexes have also demonstrated broad utility, functioning as effective catalysts in organic synthesis and finding applications across medicinal chemistry, materials science, photovoltaics, and chemical sensing

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

• this end, selected representative examples ranging from fundamental processes such as Diels–Alder or Alder–ene reactions to double-group transfer reactions or 1,3-dipolar cycloadditions involving metal complexes are presented. It is found that while more synchronous processes tend to exhibit greater

General method for the synthesis of enaminones via photocatalysis

• Paula Pérez-Ramos,
• Raquel G. Soengas and
• Humberto Rodríguez-Solla

Beilstein J. Org. Chem. 2025, 21, 1535–1543, doi:10.3762/bjoc.21.116

• the reactivity of unsaturated esters towards an aza-Michael addition is the use of transition metal complexes as catalysts/promoters [40][41][42]. Considering this background, we reasoned that Ni(II) could be a suitable catalyst for the amination of unsaturated systems. Initial investigations were

Oxetanes: formation, reactivity and total syntheses of natural products

• Peter Gabko,
• Martin Kalník and
• Maroš Bella

Beilstein J. Org. Chem. 2025, 21, 1324–1373, doi:10.3762/bjoc.21.101

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

• applications of calcium complexes with axially chiral BINOL phosphate ligands have been reported in recent years [28][32][33][34][35][36][37][38], as well as complexes with other chiral phosphoric acid ligands [39]. Since then, other main group metal complexes with BINOL phosphate ligands have been discovered

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

• -row d6 metal complexes such as Fe(II) complexes and positions Cr(0) as a promising alternative in photoredox applications under low-energy red-light conditions. The enhanced performance of these Cr(0) complexes is attributed to their strong ligand field, provided by the isocyanide ligands, which

• properties of metal complexes. Phthalocyanins, porphyrins, and their derivatives exemplify this, as their rigid macrocyclic structures enable strong absorption in the visible to NIR regions, making them appealing for photoredox catalysis applications. For instance, ruthenium phthalocyanin complexes have

• photocatalyst has shown superior yields compared to free-base and other phthalocyanin first-row transition-metal complexes, such as nickel. The choice of solvent was also critical for optimizing the reaction efficiency: a mixture of pyridine and methanol not only improved the yield but also has helped to

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

• functional versatility [44], and many of these resulting metal complexes are catalytically active [45][46][47]. These synthetic metalloporphyrins take inspiration from biological systems, such as hemes (iron complexes), chlorophylls (magnesium complexes), and vitamin B12 (cobalt complex). Contrary to

• 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

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

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

• derivatives are used as ligands in the synthesis of metal complexes (Ni(II), Pd(II), Pt(II), Cu(I), Ag(I) etc.) exhibiting antibacterial and antitumor activity [34]. In most cases, polyfunctional catechol thioethers were obtained by Michael reaction via the interaction of o-, p-benzoquinone and the

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

• and type II’ β-hairpin. Even though the latter was consistently lower in ground state energy (up to 6 kcal/mol for some catalysts), predictive models for enantioselectivity were found for both catalyst conformers in separate MLR models. For organophosphorous ligands of transition metal complexes, the

1,2-Difluoroethylene (HFO-1132): synthesis and chemistry

• Liubov V. Sokolenko,
• Taras M. Sokolenko and
• Yurii L. Yagupolskii

Beilstein J. Org. Chem. 2024, 20, 1955–1966, doi:10.3762/bjoc.20.171

• transitional metal complexes with 1,2-difluoroethylene as a ligand should be mentioned [109][110][111]. Conclusion In conclusion, our literature analysis demonstrated that radical processes are most typical for 1,2-difluoroethylene, while examples of electrophilic reactions are scarce, and nucleophilic

Benzylic C(sp³)–H fluorination

• Alexander P. Atkins,
• Alice C. Dean and
• Alastair J. J. Lennox

Beilstein J. Org. Chem. 2024, 20, 1527–1547, doi:10.3762/bjoc.20.137

• transition-metal complexes to generate metal–fluorine bonds capable of FAT to benzylic substrates. In a follow-up to their work using electrophilic fluorine sources for palladium-catalysed benzylic C–H fluorination (Figure 5), the Sanford group demonstrated in 2012 the same transformation could be achieved

Electrophotochemical metal-catalyzed synthesis of alkylnitriles from simple aliphatic carboxylic acids

• Yukang Wang,
• Yan Yao and
• Niankai Fu

Beilstein J. Org. Chem. 2024, 20, 1497–1503, doi:10.3762/bjoc.20.133

• invention of cooperative catalysis with electrochemical transition metal catalysis, which generally has mild oxidation potential for the generation of persistent radicals in the form of nucleophile-bound metal complexes. We and other groups have successfully applied this reaction design to enantioselective

Rapid construction of tricyclic tetrahydrocyclopenta[4,5]pyrrolo[2,3-b]pyridine via isocyanide-based multicomponent reaction

• Xiu-Yu Chen,
• Ying Han,
• Jing Sun and
• Chao-Guo Yan

Beilstein J. Org. Chem. 2024, 20, 1436–1443, doi:10.3762/bjoc.20.126

• carbon atom of isocyanide has both a lone electron pair and empty orbitals, so it has outstanding electrophilic and nucleophilic reactivity. At the same time, isocyanide also has good coordination ability to coordinate with metals to form diverse metal complexes [1][2][3]. Therefore, isocyanides have