Total synthesis of asperdinones B, C, D, E and terezine D

• Ravi Devarajappa and
• Stephen Hanessian

Beilstein J. Org. Chem. 2025, 21, 2730–2738, doi:10.3762/bjoc.21.210

• in the presence of the Pd catalyst. It follows that elimination and reduction must occur after Pd insertion and formation of a pallado–zinc intermediate which undergoes β-elimination and proton transfer. Seminal studies by Jackson [61] have reported related results with iodozinc N-Boc-ʟ-alanine

Thiadiazino-indole, thiadiazino-carbazole and benzothiadiazino-carbazole dioxides: synthesis, physicochemical and early ADME characterization of representatives of new tri-, tetra- and pentacyclic ring systems and their intermediates

• Gyöngyvér Pusztai,
• László Poszávácz,
• Anna Vincze,
• András Marton,
• Ahmed Qasim Abdulhussein,
• Judit Halász,
• András Dancsó,
• Gyula Simig,
• György Tibor Balogh and
• Balázs Volk

Beilstein J. Org. Chem. 2025, 21, 2220–2233, doi:10.3762/bjoc.21.169

• were previously used for the synthesis of 7-nitroindole derivatives: heating in polyphosphoric acid (PPA) at 80 °C [24][25]. However, our attempt was not successful. Experiments with zinc chloride, the most commonly used Lewis acid catalyst in Fischer indole syntheses, also failed under various

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

• norlignans hyperione A and ent-hyperione B was reported by the Deska group (Scheme 4) [33]. The synthesis commenced with a two-step conversion of ketone 22 to alkyne 23. Pd-catalyzed Tsuji-type reaction with zinc reagent 24, followed by acetonide hydrolysis, furnished allenic diol 25. Treating allenic diol

• 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

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

• characteristic of the earliest versions of this transformation. Several metals from the p- and the d-blocks of the periodic table, such as aluminum [7], indium [8], bismuth [7], zinc [9][10][11][12][13][14][15][16][17], and manganese [18][19], were later studied. The use of zinc, in particular, has attracted

• increased to 68% when DMF was used (Table 1, entry 2). The replacement of the platinum anode with graphite or zinc (Table 1, entries 4 and 5) had no significant effect on the yield. Similarly, increasing the total charge from 2.2 to 2.5 F/mol (Table 1, entries 6 and 7) resulted in only marginal changes

Systematic pore lipophilization to enhance the efficiency of an amine-based MOF catalyst in the solvent-free Knoevenagel reaction

• Pricilla Matseketsa,
• Margret Kumbirayi Ruwimbo Pagare and
• Tendai Gadzikwa

Beilstein J. Org. Chem. 2025, 21, 1854–1863, doi:10.3762/bjoc.21.144

• ][44]. Results and Discussion We opted for amine-based catalysis using our modifiable framework KSU-1, a pillared paddlewheel MOF assembled using zinc, 2-aminobenzene-1,4-dicarboxylic acid (H2BDC-NH2), and meso-α,β-di(4-pyridyl)glycol (DPG), as our parent MOF (Figure 2A). As this is a well-defined

Wittig reaction of cyclobisbiphenylenecarbonyl

• Taito Moribe,
• Junichiro Hirano,
• Hideaki Takano,
• Hiroshi Shinokubo and
• Norihito Fukui

Beilstein J. Org. Chem. 2025, 21, 1454–1461, doi:10.3762/bjoc.21.107

• S18 and Figure S19 in Supporting Information File 1). Consequently, the low g values of 3 and 5 are attributable to the offset of CD signals due to the coexistence of two conformations. Reactivity The reactivity of the Wittig products was examined. Mono-olefin 3 was treated with TiCl4 and zinc powder

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

Salen–scandium(III) complex-catalyzed asymmetric (3 + 2) annulation of aziridines and aldehydes

• Linqiang Wang and
• Jiaxi Xu

Beilstein J. Org. Chem. 2025, 21, 1087–1094, doi:10.3762/bjoc.21.86

• of racemic and optically active functionalized cis-2,5-diaryloxazolidine derivatives [13][14][15][16]. Racemic cis-2,5-diaryloxazolidine derivatives were prepared under the catalysis of zinc triflate or nickel diperchlorate (Scheme 1a) [13][14]. Later, highly enantiomeric cis-2,5-diaryloxazolidine

On the photoluminescence in triarylmethyl-centered mono-, di-, and multiradicals

• Daniel Straub,
• Markus Gross,
• Mona E. Arnold,
• Julia Zolg and
• Alexander J. C. Kuehne

Beilstein J. Org. Chem. 2025, 21, 964–998, doi:10.3762/bjoc.21.80

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

• reversed by adding zinc halides (Scheme 4). When treated with allylic phosphates 17 in the presence of ZnCl₂, these copper reagents 14 showed a dramatic shift in selectivity, favoring SN2' substitution. This exceptional reversed regioselectivity likely occurs through the in situ formation of copper–zinc

Photomechanochemistry: harnessing mechanical forces to enhance photochemical reactions

• Francesco Mele,
• Ana M. Constantin,
• Andrea Porcheddu,
• Raimondo Maggi,
• Giovanni Maestri,
• Nicola Della Ca’ and
• Luca Capaldo

Beilstein J. Org. Chem. 2025, 21, 458–472, doi:10.3762/bjoc.21.33

• zinc cations to align 1.1 through the formation of hydrogen-bonded coordination complexes. Thus, when a single crystal of the [Zn(bpe)2(H2O)4](NO3)2·8/3H2O·2/3bpe complex was exposed to UV irradiation (dark blue phosphor lamps, λ = 350 nm) for 25 h, only 46% conversion to 1.2 was observed via 1H NMR

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

• such as zinc as proposed by Furuyama et al. [35]. In this way, the authors have developed a series of phthalocyanin zinc complexes with electron-rich sulfur atoms at the non-peripheral positions of the phthalocyanin ring. This functionalization allows the destabilization of the highest occupied

• this review hitherto. This singlet oxygen is generated by the energy transfer from the excited state of the phthalocyanin zinc complexes to molecular oxygen, allowing the oxidation of the N-phenyltetrahydroisoquinoline 21 into a reactive iminium intermediate that subsequently couples with nucleophiles

• to give 22. In a same manner, Opatz et al. have shown that zinc phthalocyanins can catalyze oxidative cyanation reactions of tertiary amines 23, yielding α-aminonitriles 24 under continuous-flow conditions [36]. This reaction proceeds through the excitation of zinc phthalocyanin by near-infrared

Hydrogen-bonded macrocycle-mediated dimerization for orthogonal supramolecular polymerization

• Wentao Yu,
• Zhiyao Yang,
• Chengkan Yu,
• Xiaowei Li and
• Lihua Yuan

Beilstein J. Org. Chem. 2025, 21, 179–188, doi:10.3762/bjoc.21.10

• cooperative intermolecular forces. Zinc ion-induced coordination with the macrocycle and a terpyridinium derivative enabled orthogonal polymerization, as revealed by 1H NMR, DLS, and TEM techniques. In addition, viscosity measurements showed a transition from oligomers to polymers at the critical

• polymers (Scheme 1). The terpyridyl group and the pyridinium cation in the AB-type monomer G2 each function as a “sticker” to enable supramolecular polymerization in the presence of the macrocyclic component and zinc ions. The driving force for the recognition involves multiple cooperative interactions

• coordinating metal ions. In such supramolecular polymers, orthogonal host–guest and coordination interactions are responsible for polymerization. Host–guest complexation and zinc coordination When forming supramolecular polymers, an AB-type monomer, i.e., the guest G2, is supposed to interact with the

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

• reaction was also fruitful to obtain 1,2-dihydroisoquinolines 25 starting from 2-alkynylbenzaldehydes, primary amines and allylic or benzyl bromide, in the presence of zinc and using the combination of Mg(ClO4)2/Cu(OTf)2 as catalyst. The use of a mixture THF/DCE 1:20 as solvent was mandatory, because THF

Synthesis of extended fluorinated tripeptides based on the tetrahydropyridazine scaffold

• Thierry Milcent,
• Pascal Retailleau,
• Benoit Crousse and
• Sandrine Ongeri

Beilstein J. Org. Chem. 2024, 20, 3174–3181, doi:10.3762/bjoc.20.262

• synthesis of tripeptides incorporating new fluorinated heterocyclic hydrazino acids, based on the tetrahydropyridazine scaffold is described. Starting from simple fluorinated hydrazones, these non-proteinogenic cyclic β-amino acids were easily prepared by a zinc-catalyzed aza-Barbier reaction followed by an

• ,anti. Then, hydrazones 3 were reacted with zinc and methyl 2-(bromomethyl)acrylate (4). This aza-Barbier reaction was performed in a biphasic medium (THF/aqueous solution of saturated NH4Cl) to avoid the formation of the α-methylene-γ-lactam obtained by intramolecular cyclization of the zinc amide on

Hypervalent iodine-mediated intramolecular alkene halocyclisation

• Charu Bansal,
• Oliver Ruggles,
• Albert C. Rowett and
• Alastair J. J. Lennox

Beilstein J. Org. Chem. 2024, 20, 3113–3133, doi:10.3762/bjoc.20.258

• aza-heterocycles were synthesised in good yields. The authors proposed a mechanism for the fluorocyclisation reactions (Scheme 6), which relies on the activation of the fluoro-iodane reagent 12 with the zinc catalyst. The activation enables better orbital overlap to occur with the π bond of the alkene

Tailored charge-neutral self-assembled L₂Zn₂ container for taming oxalate

• David Ocklenburg and
• David Van Craen

Beilstein J. Org. Chem. 2024, 20, 3007–3015, doi:10.3762/bjoc.20.250

• can easily replace ligand strands leading to a partial or full receptor decomposition. Herein, we present a charge-neutral zinc(II)-based metallocontainer which was tuned to contest oxalate as most competitive dicarboxylate. The dianion is bound in a 1:1 fashion with a binding constant of log K = 4.39

• assembly is maintained. The undesired outcome is free ligand strands accompanied by simple metal oxalate complexes or unidentifiable mixtures of aggregates (Figure 1a). We observed this issue by ourselves for a self-assembled charge-neutral zinc-based container which proved otherwise to be an excellent

• dicarboxylate receptor by binding these dianions in a coordinative fashion between the zinc centers with binding constants up to log K = 8.16 [74]. However, even this very potent host was struggling with shorter dicarboxylates and with oxalate especially, resulting in an unknown mixture of species. In general

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

• Paris, France 10.3762/bjoc.20.239 Abstract The use of alkylzinc bromides in the multicomponent Mannich reaction is described. Heteroleptic organozinc compounds were obtained in THF or 2-MeTHF by direct insertion of zinc dust into the C–Br bond of alkyl bromides. It was found that the presence of a

• primary organozinc reagents. Keywords: alkyl bromides; branched amines; Mannich reaction; multicomponent reaction; zinc; Introduction The multicomponent Mannich reaction is one of the most powerful tools available in organic synthesis for the straightforward generation of α-branched amines [1][2][3

• organolithium reagents, thus limiting functional-group tolerance [11][12][13]. By contrast, heteroleptic (mixed) alkylzinc species (i.e., RZnX) are readily available and can typically be prepared from alkyl halides by direct insertion of metallic zinc into the carbon–halogen bond [14][15][16][17][18][19][20][21

Access to optically active tetrafluoroethylenated amines based on [1,3]-proton shift reaction

• Yuta Kabumoto,
• Eiichiro Yoshimoto,
• Bing Xiaohuan,
• Masato Morita,
• Motohiro Yasui,
• Shigeyuki Yamada and
• Tsutomu Konno

Beilstein J. Org. Chem. 2024, 20, 2776–2783, doi:10.3762/bjoc.20.233

• ]-proton shift reaction of various tetrafluoroethylenated imines. Results and Discussion The preparation of substrates used in this study was as outlined in Scheme 3. Namely, the zinc reagent was prepared from commercially available 3,3,4,4-tetrafluoro-1-butene (18) [33] and reacted with various acid

Efficient one-step synthesis of diarylacetic acids by electrochemical direct carboxylation of diarylmethanol compounds in DMSO

• Hisanori Senboku and
• Mizuki Hayama

Beilstein J. Org. Chem. 2024, 20, 2392–2400, doi:10.3762/bjoc.20.203

• (Table 1, entry 6). In contrast, zinc was not effective as an anode material in the carboxylation, probably due to competitive electrochemical reduction of zinc ions generated by electrochemical oxidation of the zinc anode. The deposition of a black precipitate was observed visually at the cathode (Table

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

• ,β-unsaturated imines 9. However, with ethynylimines 12, the enantioselectivity dropped to a modest level. In addition, the reaction with sterically hindered tertiary allylboronates, such as the chiral (R)-α-cyclohexyl-α-methyl-allylboronate required the use of catalytic amounts of zinc tert-butoxide

Electrochemical allylations in a deep eutectic solvent

• Sophia Taylor and
• Scott T. Handy

Beilstein J. Org. Chem. 2024, 20, 2217–2224, doi:10.3762/bjoc.20.189

• (entry 1) resulted in good conversion to the allylation product, while zinc, magnesium, and graphite (Table 1, entries 3–5) displayed no reaction at all. This observation was somewhat surprising considering that both zinc and tin are very commonly used in conventional allylations in addition to as

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

• of IBX ensured the completion of the reaction sequence [96]. A notable advantage of this method is the ability to reuse the catalyst multiple times. In addition to Yb(PFO)3, zinc triflate can also serve as an effective catalyst for the synthesis of pyrazoles 65. It also catalyzes the oxidation of

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

• -difluoroethylene was based on 1,2-dichloro-1,2-difluoroethane (HCFC-132) [48][49][50][51][52], prepared from 1,1,2,2-tetrachloro-1,2-difluoroethane (CFC-112) by reduction using lithium aluminum hydride [48][49][50][51] or photoreduction (Scheme 2) [51]. The resulting HCFC-132 reacted with zinc [47][49][52] or

Negishi-coupling-enabled synthesis of α-heteroaryl-α-amino acid building blocks for DNA-encoded chemical library applications

• Matteo Gasparetto,
• Balázs Fődi and
• Gellért Sipos

Beilstein J. Org. Chem. 2024, 20, 1922–1932, doi:10.3762/bjoc.20.168

• of ethyl 2-bromoacetate through a pre-activated zinc column (see page 11 in Supporting Information File 1) [44]. The Reformatsky reagent could be obtained in yields varying from 70 to 90% depending on the activation state of the column. The yield of the reaction was determined by titration with

• subsequent re-esterification was necessary to achieve the desired ketoester. Reduction of the oximes Oximes are commonly reduced to the corresponding amines using either palladium on activated carbon and hydrogen gas [65][66][67][68], or with zinc and a Brønsted acid as source of hydrogen [68][69]. Both

• methods were tested and after a brief optimization process, zinc dust and HCl in a mixture of EtOH/dioxane proved to be the best conditions in order to maximize the yield and limit the amino ester instability issues (see Table S6 in Supporting Information File 1). By slightly adjusting the reaction time