Studies on the syntheses of β-carboline alkaloids brevicarine and brevicolline

• Benedek Batizi,
• Patrik Pollák,
• András Dancsó,
• Péter Keglevich,
• Gyula Simig,
• Balázs Volk and
• Mátyás Milen

Beilstein J. Org. Chem. 2025, 21, 955–963, doi:10.3762/bjoc.21.79

• , Semmelweis University, Üllői út 26, H-1085 Budapest, Hungary 10.3762/bjoc.21.79 Abstract A new total synthesis of the β-carboline alkaloid brevicarine is disclosed. The synthesis was carried out starting from an aromatic triflate key intermediate, allowing the introduction of various substituents into

• salt for further confirming their structures. A new synthesis of the related alkaloid brevicolline was also attempted from the same intermediate. However, after successful coupling of β-carboline with N-methylpyrrole, the trials to saturate the pyrrole ring under various conditions led to unexpected

• chemistry of β-carbolines [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] has now focused our attention on these two alkaloids. In a recent publication we disclosed a new total synthesis of racemic brevicolline ((±)-1) (Scheme 1) [9]. A prerequisite for the synthesis was the development of a new

Study of tribenzo[b,d,f]azepine as donor in D–A photocatalysts

• Katy Medrano-Uribe,
• Jorge Humbrías-Martín and
• Luca Dell’Amico

Beilstein J. Org. Chem. 2025, 21, 935–944, doi:10.3762/bjoc.21.76

• chemistry and photocatalysis is the carbazolyl dicyanobenzene (CDCB) family. Since the initial report on the synthesis and photoluminescence study of 4CzIPN (1, Figure 1a) [6], the scientific community has recognized its potential under photocatalytic manifolds. This interest is attributed to: i) its

• interesting photophysical properties compared to common substrates like c, diphenylamine (d), and phenoxazine (e) [28][29][30]. However, their potential as D-unit in organic PCs remains unexplored. For this reason, studying this avenue could unlock new opportunities for the synthesis and design of more

• powerful, efficient and versatile organic photocatalysts. We herein present the design, synthesis and study of a new sulfur-based D–A family using diverse nitrogen donors (Figure 1b). We performed complete photophysical characterization of the diverse D–A molecules to analyze the structure–properties

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

• the benzylic alcohol, a 1,2-Grignard addition and an AcOH-interrupted Nazarov cyclization. Keywords: enantioselective synthesis; interrupted Nazarov cyclization; khayanolide-type limonoids; tetracyclic framework; Introduction Limonoids, a class of tetranortriterpenoids derived biosynthetically from

• synthesis of azadiradione (1). Following this, Ley and his team successfully synthesized azadirachtin (2) in 2007, a limonoid extensively utilized in organic agriculture [11]. In recent years, remarkable progress has been made on the total syntheses of various limonoids, with notable contributions from

• their total synthesis. Two synthetic studies were disclosed successively by Sarpong [27] and Jirgensons [28], both focusing on the construction of the unique methanoindene cage structure (A1A2B ring system). Building upon our previous syntheses of phragmalin-type limonoids [29], we herein disclose a

Silver(I) triflate-catalyzed post-Ugi synthesis of pyrazolodiazepines

• Muhammad Hasan,
• Anatoly A. Peshkov,
• Syed Anis Ali Shah,
• Andrey Belyaev,
• Chang-Keun Lim,
• Shunyi Wang and
• Vsevolod A. Peshkov

Beilstein J. Org. Chem. 2025, 21, 915–925, doi:10.3762/bjoc.21.74

• procedures and harsh reaction conditions, resulting in limited substituent and scaffold diversity [18][19]. In this regard, multicomponent reactions (MCRs) have gained increasing attention for their operational simplicity, efficiency, robustness, atom economy, and potential for diversity-oriented synthesis

• ]. In 2015, García-Valverde and co-workers described an alternative synthesis of benzo[e][1,4]diazepines 6, exploring the nitro group of 2-nitrobenzoic acid as a masked amino group. The release was achieved through the post-Ugi reduction of the nitro group with SnCl2 triggering concomitant

• ][44] and hydroalkoxylations [45]. In 2013, Van der Eycken and co-workers described an intramolecular cationic gold-catalyzed post-Ugi heteroannulation of imidazoles with activated alkynes for the diversity-oriented synthesis of imidazo[1,4]diazepines 13 from Ugi-derived propargylamides 12 (Scheme 1c

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

• reaction activity and selectivity differentiation, the review provides a systematic analysis of the mechanisms of critical steps through specific case studies. It is hoped that the controllable/divergent synthesis concept will spark the interest of practitioners and aficionados to delve deeper into the

• discipline and pursue novel advancements in the realm of chemical synthesis. Keywords: controllable; divergent; diverse products; switchable synthesis; Introduction In the era of synthetic organic chemistry, divergence can produce stereodivergence (including diastereodivergence and enantiodivergence) [1][2

• increasingly attracted attention [5][7][8][9][10][11][12][13][14], for example, in 2024, Rana [15] and co-workers reported advances in solvent-controlled stereodivergent catalysis. Surprisingly, to our knowledge, there is currently no comprehensive review of studies on controllable/divergent synthesis. This

Dicarboxylate recognition based on ultracycle hosts through cooperative hydrogen bonding and anion–π interactions

• Wen-Hui Mi,
• Teng-Yu Huang,
• Xu-Dong Wang,
• Yu-Fei Ao,
• Qi-Qiang Wang and
• De-Xian Wang

Beilstein J. Org. Chem. 2025, 21, 884–889, doi:10.3762/bjoc.21.72

• cellular metabolism; they regulate the activity of numerous enzyme receptors, and serve as intermediates in the synthesis of more complex biomolecules [21]. However, excessive consumption or production, as well as insufficient clearance of dicarboxylates, can lead to various health problems [22

• binding sites to enhance anion binding [30]. The recognition capabilities of these ultracycles toward a range of dicarboxylates were successfully demonstrated. Results and Discussion Synthesis and structure The ultracycles B4aH, B5aH, and B6aH were synthesized following the previously reported procedure

• . Synthesis of ultracycles. Supporting Information Supporting Information File 4: Experimental details and characterization data (including 1H NMR, 13C NMR, IR, and HRMS of precursor compounds and ultracycles, X-ray data for B4aH, theoretical calculations, and NMR titration data). Funding Financial support

Cu–Bpin-mediated dimerization of 4,4-dichloro-2-butenoic acid derivatives enables the synthesis of densely functionalized cyclopropanes

• Patricia Gómez-Roibás,
• Andrea Chaves-Pouso and
• Martín Fañanás-Mastral

Beilstein J. Org. Chem. 2025, 21, 877–883, doi:10.3762/bjoc.21.71

• versatile building blocks for the stereoselective synthesis of chlorocyclopropanes. Keywords: chlorocyclopropanes; copper; cyclization; 4,4-dichloro-2-butenoic acid derivatives; dimerization; Introduction In the last years our group has been focused on the development of catalytic methodologies for the

• ). We have studied this reaction and now report a catalytic methodology for the diastereoselective synthesis of these dimeric structures. The high degree of functionalization present in these molecules, which feature two ester groups, an aliphatic gem-dichloride and a dichloroalkene unit, offers ample

• mechanism for the Cu-catalyzed dimerization of 4,4-dichoro-2-butenoic acid derivatives. a) KOt-Bu-mediated intramolecular cyclization of 9. b) Direct formation of cyclopropane 20 from gem-dichloride 5 using KOt-Bu as base. Optimization studies. Synthesis of densely functionalized (2,2-dichlorovinyl

Data accessibility in the chemical sciences: an analysis of recent practice in organic chemistry journals

• Sally Bloodworth,
• Cerys Willoughby and
• Simon J. Coles

Beilstein J. Org. Chem. 2025, 21, 864–876, doi:10.3762/bjoc.21.70

• share their data, to take advantage of recent advances in machine learning (ML) for synthesis planning, reaction optimization, and property prediction [30][31][32]. The discoverability and reusability of data, especially by machines, is central to the ‘FAIR Guiding Principles for scientific data

• findings suggest about the impact of author guidelines upon researcher practice. Methods 12 Specialist journals with a broad scope around the central discipline of synthesis, catalysis, and methods development in organic chemistry were selected for analysis (Table 1). Criteria for journal selection are

• primary data were not deposited in a public repository (Figure 5a). Except for one example from Synthesis, data of any type had only been shared to a public repository when published in one of the four ACS journals. 95% of these used Figshare [40], (Figure 5b), and this is entirely publisher-led behavior

Light-enabled intramolecular [2 + 2] cycloaddition via photoactivation of simple alkenylboronic esters

• Lewis McGhie,
• Hannah M. Kortman,
• Jenna Rumpf,
• Peter H. Seeberger and
• John J. Molloy

Beilstein J. Org. Chem. 2025, 21, 854–863, doi:10.3762/bjoc.21.69

• activate organic molecules has had a profound impact on contemporary synthesis, enabling the practitioner to strategically construct molecules that are higher in energy from simple feedstock commodities [1][2][3][4][5]. Indeed, the unique ability to access high energy intermediates leveraging light, has

• facilitate the synthesis of boron-containing cyclobutanes [53][54][55], excitation of these motifs to form a triplet diradical, and its application in a synthetic process, is conspicuously underexplored, presumably due to unreachable excited states and poor lifetimes when limited to a single boron unit

• identify a suitable catalyst and boron residue, while control reactions and mechanistic studies support the proposed sensitization. The platform enables direct access to mono- and vicinal cyclobutylboronic esters that could be effectively derivatized to demonstrate their potential in synthesis. Results and

Unraveling cooperative interactions between complexed ions in dual-host strategy for cesium salt separation

• Zhihua Liu,
• Ya-Zhi Chen,
• Ji Wang,
• Qingling Nie,
• Wei Zhao and
• Biao Wu

Beilstein J. Org. Chem. 2025, 21, 845–853, doi:10.3762/bjoc.21.68

• individual anion or cation receptors [21]. An alternative approach for ion separation involves the combination of an anion receptor and a cation receptor, known as the dual-host strategy [22][23][24]. Unlike ion-pair receptors, this strategy avoids the intricate, multi-step synthesis required for designing

Chitosan-supported CuI-catalyzed cascade reaction of 2-halobenzoic acids and amidines for the synthesis of quinazolinones

• Xuhong Zhao,
• Weishuang Li,
• Mengli Yang,
• Bojie Li,
• Yaoyao Zhang,
• Lizhen Huang and
• Lei Zhu

Beilstein J. Org. Chem. 2025, 21, 839–844, doi:10.3762/bjoc.21.67

• 10.3762/bjoc.21.67 Abstract A chitosan-supported CuI (CS@CuI) catalyst was developed for the synthesis of quinazolinones from 2-halobenzoic acids (including iodine and bromine) and amidines. The reaction proceeds under mild reaction conditions, demonstrating a broad substrate scope (30 examples) and good

• promote this cascade reaction for the synthesis of quinazolinones without the need for additional ligands or additives (Scheme 1a) [7][10]. Since then, various copper-based catalysts, both homogeneous and heterogeneous, have been explored (Scheme 1b) [11][12][13][14][15][16]. For example, Wang’s group

• developed a magnetically recoverable and reusable Fe3O4 nanoparticle-supported copper(I) catalyst with excellent catalytic efficiency for quinazolinone synthesis [11]. In addition, Cai et al. reported that MCM-41-immobilized tridentate nitrogen-supported copper(I) [MCM-41-3N–CuI] served as a highly

Substituent effects in N-acetylated phenylazopyrazole photoswitches

• Radek Tovtik,
• Dennis Marzin,
• Pia Weigel,
• Stefano Crespi and
• Nadja A. Simeth

Beilstein J. Org. Chem. 2025, 21, 830–838, doi:10.3762/bjoc.21.66

• %). Results and Discussion Synthesis The PAPs in this study were obtained in a straightforward, three-step metal-free synthesis from commercially available aniline derivatives adapting known procedures [31][38]. An overview of the compounds used in this study and their synthesis is displayed in Scheme 1

• structural modifications affect the synthesis, photochemical, and thermal behavior of PAP derivatives introducing NAc-PAPs as novel compound set with enhanced photochemical performance. Our findings provide valuable guidance for designing functional PAPs with tailor-made photochemistry and photophysical

4-(1-Methylamino)ethylidene-1,5-disubstituted pyrrolidine-2,3-diones: synthesis, anti-inflammatory effect and in silico approaches

• Nguyen Tran Nguyen,
• Vo Viet Dai,
• Luc Van Meervelt,
• Do Thi Thao and
• Nguyen Minh Thong

Beilstein J. Org. Chem. 2025, 21, 817–829, doi:10.3762/bjoc.21.65

• , Vietnam Academy of Science and Technology (VAST), Hanoi 10072, Vietnam 10.3762/bjoc.21.65 Abstract Pyrrolidine-2,3-diones are important intermediates in the synthesis of numerous nitrogen-containing heterocycles which possess a broad spectrum of biological and pharmacological activities. In this article

• , we report the synthesis of 4-(1-methylamino)ethylidene-1,5-disubstituted pyrrolidine-2,3-diones via a reversible transimination reaction between Schiff’ base (C=N) linkage-containing pyrrolidine-2,3-dione derivatives and methylamine with yields of 80 to 92%. In addition to nuclear magnetic resonance

• intermediates in the synthesis of 2-pyrrolidinone ring containing bioactive medicinal compounds [18]. In this article, we report the accidental synthesis of 4-(1-methylamino)ethylidene-1,5-disubstituted pyrrolidine-2,3-dione derivatives via the transimination reaction between 4-[1-(4-methoxybenzyl)amino

Synthesis and photoinduced switching properties of C₇-heteroatom containing push–pull norbornadiene derivatives

• Daniel Krappmann and
• Andreas Hirsch

Beilstein J. Org. Chem. 2025, 21, 807–816, doi:10.3762/bjoc.21.64

• Daniel Krappmann Andreas Hirsch Department Chemistry and Pharmacy, Friedrich-Alexander-Universität Erlangen-Nürnberg, Nikolaus-Fiebiger Straße 10, 91058 Erlangen, Germany 10.3762/bjoc.21.64 Abstract We report the synthesis and characterization of heteroatom-incorporated norbornadiene (NBD

• intermediates in total [29][30] and bio-synthesis protocols [31], e.g., in inositol chemistry [32] or towards aminocyclitols [33]. The potential of these compounds as functional photoswitches was primarily assessed in the 1960s and 1970s by Prinzbach and co-workers, who identified a variety of rearrangement

• incorporating larger heteroatoms in the bridge moiety, we anticipate a bathochromic shift that would facilitate absorption match with the solar emission spectrum. Results and Discussion Synthesis The library of new heterocyclic NBD molecules synthesized and investigated in this study is presented in Scheme 1

Regioselective formal hydrocyanation of allenes: synthesis of β,γ-unsaturated nitriles with α-all-carbon quaternary centers

• Seeun Lim,
• Teresa Kim and
• Yunmi Lee

Beilstein J. Org. Chem. 2025, 21, 800–806, doi:10.3762/bjoc.21.63

• conditions and shows broad applicability to di- and trisubstituted allenes. Its practicality is demonstrated through the gram-scale synthesis and functional group transformations of amines, amides, and lactams, emphasizing its versatility and synthetic significance. Keywords: α-quaternary nitrile; Cu

• are important intermediates in organic syntheses because of the versatility of the cyano group, which can be readily transformed into a wide range of functional groups, including amides, carboxylic acids, amines, aldehydes, ketones, and N-heterocycles [6][7][8]. However, the synthesis of all-carbon

• with diverse functional groups [12][13][14]. Consequently, the development of selective and predictable strategies for the introduction of cyano groups into quaternary carbon frameworks has become necessary in organic synthesis. The transition-metal-catalyzed hydrocyanation of carbon–carbon double

Recent advances in the electrochemical synthesis of organophosphorus compounds

• Babak Kaboudin,
• Milad Behroozi,
• Sepideh Sadighi and
• Fatemeh Asgharzadeh

Beilstein J. Org. Chem. 2025, 21, 770–797, doi:10.3762/bjoc.21.61

• synthesis of various organophosphorus compounds through the formation of phosphorus–carbon, phosphorus–nitrogen, phosphorus–oxygen, phosphorus–sulfur, and phosphorus–selenium bonds. The impact of different electrodes is also discussed in this matter. Graphite, platinum, RVC, and nickel electrodes have been

• used extensively for the electrochemical synthesis of organophosphorus compounds. The recent advances in the electrochemical synthesis of organophosphorus compounds have made this method a promising method for preparing various structures. This review is an introduction to encourage scientists to use

• electrosynthesis as a green, precise, and low-cost method to prepare phosphorous structures. Keywords: electrosynthesis; green synthesis; organophosphorus compounds; P–C bond formation; P–heteroatom bond formation; Introduction The electrochemical synthesis is a valuable and beneficial method for the preparation

New advances in asymmetric organocatalysis II

• Radovan Šebesta

Beilstein J. Org. Chem. 2025, 21, 766–769, doi:10.3762/bjoc.21.60

• as the eco- and user-friendliness of asymmetric organocatalysis contribute to its growing applicability in the synthesis of complex target molecules, such as therapeutic agents [17][18]. However, nowadays organocatalysis does go well beyond the boundaries of organic chemistry. This can also be seen

• Malkov reviewed the recent progress in the organocatalytic synthesis of chiral homoallylic amines. This important structural motif is typically made by asymmetric allylation of imines, and the authors describe various catalytic approaches as well as applications of these strategies in total synthesis [25

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

• hydrocyanation of hydrazones, catalyzed by a calcium–BINOL phosphate complex, has been studied for the first time both experimentally and computationally with DFT methods. A full catalytic cycle for the enantioselective synthesis of α-hydrazinonitriles is proposed based on insights gained from DFT calculations

• enantioselectivity achieved with the calcium catalyst remains modest, mainly due to competing pathways for the Z- and E-hydrazone isomers leading to opposite enantiomers. The experimental results confirm these computational proposals. Keywords: asymmetric synthesis; calcium–BINOL phosphate catalysis; hydrocyanation

• through calcium catalysis [8][9][10]. Asymmetric synthesis has also been achieved via, e.g., 1,4-addition and [3 + 2] cycloaddition of 3-tetrasubstituted oxindoles with a calcium Pybox catalyst [11][12], or through enantioselective Friedel–Crafts and carbonyl–ene reactions [13]. Since the pioneering

Copper-catalyzed domino cyclization of anilines and cyclobutanone oxime: a scalable and versatile route to spirotetrahydroquinoline derivatives

• Qingqing Jiang,
• Xinyi Lei,
• Pan Gao and
• Yu Yuan

Beilstein J. Org. Chem. 2025, 21, 749–754, doi:10.3762/bjoc.21.58

• report the copper-catalyzed synthesis of tetrahydroquinoline derivatives via a domino reaction of aniline with cyclobutanone oxime. This method demonstrates a selective approach for generating bioactive tetrahydroquinoline scaffolds, which have broad applications in pharmaceutical chemistry. The reaction

• the desired product. Keywords: copper catalysis; cyclobutane-fused tetrahydroquinolines; domino cyclization reaction; green synthesis; Introduction Tetrahydroquinolines (THQs) represent a privileged scaffold in medicinal chemistry, exhibiting a broad spectrum of biological activities and serving as

• therapeutic development. The strained cyclobutane ring, in particular, acts as a versatile and conformationally constrained building block, enabling the construction of complex molecular architectures with potent biological activities [22]. Despite their promise, the synthesis of cyclobutane-fused THQs

Orthogonal photoswitching of heterobivalent azobenzene glycoclusters: the effect of glycoligand orientation in bacterial adhesion

• Leon M. Friedrich and
• Thisbe K. Lindhorst

Beilstein J. Org. Chem. 2025, 21, 736–748, doi:10.3762/bjoc.21.57

• potency as inhibitors of Man-specific bacterial adhesion investigated. Results and Discussion Synthesis For the preparation of the homobivalent glycocluster 6αMan3αMan 2, the known mannosyl thioacetate 7 [31] was prepared from the trichloroacetimidate 6 [32] and thioacetic acid in an α-selective reaction

• 3-O-(mannosyloxyazobenzene)-6-thio-mannoside 11 was employed, which was prepared according to a known procedure applied for the synthesis of the heterobivalent glycocluster 6βGlc3αMan 1 (cf. Supporting Information File 1, Scheme S1). The cross-coupling of thiol 11 with the azobenzene

• α-ᴅ-mannopyranosyloxyazobenzene mannosides 6βGlc 3 and 6αMan 4 were prepared first (Scheme 2A). The synthesis of the β-ᴅ-glucopyranosyl mannoside 6βGlc 3 started from the literature-known S,O-acetylated mannoside 13 [35], which was chemoselectively deprotected at the 6-position employing DTT (1,4

Synthesis of HBC fluorophores with an electrophilic handle for covalent attachment to Pepper RNA

• Raphael Bereiter and
• Ronald Micura

Beilstein J. Org. Chem. 2025, 21, 727–735, doi:10.3762/bjoc.21.56

• )cyanophenylacetonitrile) fluorophores for easy access, which will contribute to the rapid dissemination of the RNA imaging approaches associated therewith. Keywords: covalent RNA labeling; FLAP; fluorophore synthesis; HBC530; self-alkylating ribozymes; Introduction The discovery of fluorescent reporters, such as green

• research group has recently developed the first covalent FLAP system (coFLAP) based on the Pepper aptamer and demonstrated some advantages of the covalent (coPepper) over the non-covalent (Pepper) reporter in RNA imaging (Figure 1) [11]. Here, we describe the full synthesis of “self-attaching” Pepper

• have shown that this feature can be exploited to construct a covalent bond between the fluorophore and the RNA by replacing the N-hydroxyethyl group of the dye with an electrophilic handle, resulting in efficient RNA alkylation at the N7 of G41 [11]. Synthesis and evaluation of Pepper dyes with an

Acyclic cucurbit[n]uril bearing alkyl sulfate ionic groups

• Christian Akakpo,
• Peter Y. Zavalij and
• Lyle Isaacs

Beilstein J. Org. Chem. 2025, 21, 717–726, doi:10.3762/bjoc.21.55

• Christian Akakpo Peter Y. Zavalij Lyle Isaacs Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, United States 10.3762/bjoc.21.55 Abstract We report the synthesis and characterization of a new acyclic cucurbit[n]uril (CB[n]) host C1 that features four

• supramolecular chemistry involves the synthesis of macrocyclic hosts and studies of their molecular recognition properties. The most widely studied macrocyclic host systems include those created entirely by covalent bonds (crown ethers, cyclodextrins, calixarenes, cyclophanes, pillararenes, cucurbit[n]urils (CB

• modular synthesis, acyclic CB[n] can be easily modified synthetically [42][43][44][45][46][47][61]. Acyclic CB[n]-type receptors featuring different length glycoluril oligomers (monomer–pentamer) and different aromatic walls (e.g., naphthalene, anthracene, triptycene) have been studied [42][62][63][64][65

Photochemically assisted synthesis of phenacenes fluorinated at the terminal benzene rings and their electronic spectra

• Yuuki Ishii,
• Minoru Yamaji,
• Fumito Tani,
• Kenta Goto,
• Yoshihiro Kubozono and
• Hideki Okamoto

Beilstein J. Org. Chem. 2025, 21, 670–679, doi:10.3762/bjoc.21.53

• the corresponding parent phenacenes PIC, FUL, and 7PHEN to reveal the effects of the fluorination at the terminal rings. Results and Discussion Synthesis of F8-phenacenes The synthetic routes to building blocks 10, 13, and 15 and those to the desired F8PIC, F8FUL, and F87PHEN are respectively shown in

• state. The orange and blue sites, respectively, indicate negative and positive regions (−0.02 ≈ 0.02 hartree). Synthesis of building blocks 10, 13, and 15. Reagents and conditions: a) NaBH4, MeOH, THF, reflux; b) PBr3, reflux; c) N-methylmorpholine-N-oxide, THF, reflux; d) ethylene glycol, p-TsOH

• , toluene, reflux; e) tert-BuLi, DMF, THF, −78 °C; f) KOH, 18-crown-6, CH2Cl2, reflux (rt for 8); g) hν, I2, cyclohexane (toluene/THF mixture for 11); h) p-TsOH, acetone, reflux. Synthesis of F8PIC, F8FUL, and F87PHEN. Reagents and conditions: a) KOH, 18-crown-6, CH2Cl2, reflux; b) hν, I2, toluene, rt

Asymmetric synthesis of fluorinated derivatives of aromatic and γ-branched amino acids via a chiral Ni(II) complex

• Maurizio Iannuzzi,
• Thomas Hohmann,
• Michael Dyrks,
• Kilian Haoues,
• Katarzyna Salamon-Krokosz and
• Beate Koksch

Beilstein J. Org. Chem. 2025, 21, 659–669, doi:10.3762/bjoc.21.52

• diastereomerically pure γ‑branched fluorinated amino acids. This work further underlines the importance of chiral Ni(II) complexes in the synthesis of fluorinated amino acids. Keywords: chiral nickel complexes; fluorinated amino acids; gram-scale amino acid synthesis; stereoselective synthesis; Introduction Non

• chiral nickel complexes. In recent years, the Soloshonok working group demonstrated the synthesis of non‑natural amino acids using the corresponding chiral Ni(II) complex [7]. In addition to the high enantiomeric purity of the corresponding products, the scale of the reaction, which extends into the

• ) complex with the corresponding fluorinated alkyl iodide. The aryl moiety of the Ni(II) complex blocks the top face of the complex, ensuring the high diastereoselectivity of this transformation. In principle, synthesis on a gram-scale permits the study of highly fluorinated systems. Recently, we introduced

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

• Abstract The transition-metal-catalyzed asymmetric allylic substitution represents a pivotal methodology in organic synthesis, providing remarkable versatility for complex molecule construction. Particularly, the generation and utilization of chiral secondary alkylcopper species have received considerable

• secondary organocopper; copper-mediated reaction; stereoselectivity; Introduction The transition-metal-catalyzed regio- and enantioselective allylic substitution represents a pivotal methodology in organic synthesis, providing remarkable versatility for complex molecule construction [1][2][3][4]. The

• 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