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Search for "catalytic" in Full Text gives 1616 result(s) in Beilstein Journal of Organic Chemistry. Showing first 200.
Oxetanes: formation, reactivity and total syntheses of natural products
Beilstein J. Org. Chem. 2025, 21, 1324–1373, doi:10.3762/bjoc.21.101
- /Williamson etherification sequence (Scheme 8) [43]. In this case, however, the radicals were generated by irradiation of α-acetyloxy iodides 36, formed by treating the corresponding ketone precursors with acetyl iodide in the presence of catalytic Zn(OTf)2. The radical addition employed electron-rich alkenes
- catalysis and proceed through a double addition mechanism. In 2011, Mikami et al. developed a catalytic asymmetric oxetane synthesis from silyl enol ethers 89 and trifluoropyruvate 90 using a chiral Cu(II) complex (Scheme 24) [67]. Besides excellent yields, they also observed very high cis/trans ratios and
- addition of the aryl halide, the disubstituted oxetane product is generated by a reductive elimination. Finally, the two catalytic cycles are closed by an oxidation/reduction process: the Fe(II) species is reoxidised by atmospheric oxygen and the Ni(I) complex is reduced by the added manganese powder. In
Recent advances in amidyl radical-mediated photocatalytic direct intermolecular hydrogen atom transfer
Beilstein J. Org. Chem. 2025, 21, 1306–1323, doi:10.3762/bjoc.21.100
- demonstrated a decent methodology of organic synthesis. These elegant strategies presented powerful C–H bond transformation toolkits (Figure 1b) [6][7][8]. One of the exceptions to the perfection is the pre-functionalization of substrates. Current catalytic methodologies predominantly rely on substrate
- prefunctionalization through directing group (DG) incorporation, inevitably necessitating covalent DG-metal coordinative anchoring. This prerequisite fundamentally compromises both atomic efficiency and synthetic practicality, thereby imposing fundamental constraints on the catalytic system's intrinsic sustainability
- in synchrony with the photocatalytic cycle, thereby allowing these HRPs to be consistently employed for catalytic equivalence. In 2016, Knowles’ group independently developed an oxidative photocatalytic system capable of directly generating amidyl radicals from N-ethyl-4-methoxybenzamide, utilizing
Recent advances and future challenges in the bottom-up synthesis of azulene-embedded nanographenes
Beilstein J. Org. Chem. 2025, 21, 1272–1305, doi:10.3762/bjoc.21.99
- dimerization of alkynes, followed by the expansion of a phenyl ring leading to the formation of an azulene moiety, was first reported over half a century ago. These reactions can be carried out using various catalytic systems, including sulfenyl chloride/AlCl3 [50], palladium catalysts [51] or gold catalysts
- azulene skeleton from a benzenoid alkyne derivative occurred when a catalytic amount of PtCl2 was used. A more systematic approach to [5]-, [6]-, and [7]helicenes with embedded azulene units was reported recently by Gao, Yang, and co-workers (Scheme 20) [100]. Alkyne precursors 154–156 were annulated
Recent advances in oxidative radical difunctionalization of N-arylacrylamides enabled by carbon radical reagents
Beilstein J. Org. Chem. 2025, 21, 1207–1271, doi:10.3762/bjoc.21.98
- activated alkenes involving benzylic C(sp3)–H bonds through a cascade cyclization process (Scheme 1) [2]. This organomediated approach can be facilitated by a catalytic amount of Lewis acid. Using DTBP as the oxidant and IrCl3 as the promoter, a range of benzylic C–H bonds in arylmethanes
- alkyl radical intermediate 1. Subsequently, radical cyclization and deprotonation, assisted by the tert-butoxy radical, led to the desired products 26. It is important to emphasize that TBHP plays a crucial role as an oxidant in regenerating the photocatalyst for the catalytic cycle. In the same year
- , Wang and his group reported an electrochemically induced intramolecular radical cyclization of N-arylacrylamides with dimethyl 2-fluoromalonate as a monofluoroalkyl radical precursor, affording fluorinated 2-oxindoles in synthetically useful yields (Scheme 15) [10]. In this system, catalytic Cp2Fe was
Synthetic approach to borrelidin fragments: focus on key intermediates
Beilstein J. Org. Chem. 2025, 21, 1135–1160, doi:10.3762/bjoc.21.91
- ]. Their method was based on the concept of “catalytic total synthesis”, wherein all stereocenters were installed under the control of catalysts. Minnaard and Madduri proposed the synthesis of the C1–C11 fragment from unsaturated thioester 92 through iterative, previously developed asymmetric 1,4-addition
- and deprotection steps, functional group transformations, stereocontrolled allylation, cross-metathesis, and Horner–Wadsworth–Emmons (HWE) olefination. This method highlights the power of catalytic stereocontrol, achieving the complex architecture of borrelidin fragments with efficiency and precision
- . The synthesis commenced with the treatment of precursor 92, obtained in three steps from ethylene glycol, with MeMgBr and catalytic 94/CuBr, yielding the 1,4-addition product 93 in 96% yield and excellent regioselectivity (ee 98%) (Scheme 15). The authors highlighted the scalability of this reaction
A versatile route towards 6-arylpipecolic acids
Beilstein J. Org. Chem. 2025, 21, 1104–1115, doi:10.3762/bjoc.21.88
- , heterogeneous catalytic hydrogenation of the enamine with palladium on carbon was chosen. While the hydride reduction of the acyliminium intermediate gave a nearly 1:1 diastereomer ratio, a 9:1 ratio was obtained for the catalytic hydrogenation (Scheme 4). While the hydride reduction of the N-acyliminium
- species did not show any significant diastereofacial discrimination, the catalytic hydrogenation occurs stereospecifically, particularly in the case of hydrogenation with palladium on carbon [49][50][51][52]. In this case, we propose that the restraints exerted by the first stereocenter lead to a
- obtained by catalytic hydrogenation, assigned as (2R,6R)-9, gave a single set of signals (Figure 1). Based on the observed coupling constants for (2R,6R)-9, H2 adopts an equatorial position as indicated by the coupling constants 3J(H2,H3,pro-R) = 2.2 Hz and 3J(H2,H3,pro-S) = 6.3 Hz, corresponding to
Salen–scandium(III) complex-catalyzed asymmetric (3 + 2) annulation of aziridines and aldehydes
Beilstein J. Org. Chem. 2025, 21, 1087–1094, doi:10.3762/bjoc.21.86
- derivatives were obtained under asymmetric catalysis with a Ni(II)–bisoxazoline complex [15] and a Nd(OTf)3/N,N'-dioxide/LiNTf2 delay catalytic system [16], respectively (Scheme 1b and c). However, further exploration for convenient asymmetric catalytic synthetic methods is still in demand because the former
- of the catalyst for the next catalytic cycle. The electron-deficient aromatic aldehydes exhibit excellent stereoselectivity due to the π-stacking interaction between their aryl group and the electron-rich malonate group. Similar π-stacking interaction-controlled stereoselectivities were observed in
- method uses readily available salen as chiral ligand, which coordinates with scandium triflate to generate a salen–Sc complex acting as efficient catalyst. The catalytic asymmetric (3 + 2) annulation of dialkyl 3-aryl-1-sulfonylaziridine-2,2-dicarboxylates and aldehydes generated optically active
Recent advances in synthetic approaches for bioactive cinnamic acid derivatives
Beilstein J. Org. Chem. 2025, 21, 1031–1086, doi:10.3762/bjoc.21.85
- applications in the pharmaceutical industry. In addition, innovative synthetic methodologies, including environmentally sustainable approaches [21][22][23], advanced catalytic systems [24][25][26], photocatalysis [27][28][29], and cutting-edge technologies, such as flow chemistry [30][31], have contributed
- with a catalytic base has also been applied to prepare cinnamate esters. For example, Heller and co-workers (2021) synthesized the ester 141 catalyzed by DBU which functioned as a Brønsted base for the alcohol (Scheme 43A) [81]. Impressively, the method could be scaled up to a multigram scale
- . Similarly, Rajendran and Rajan (2024) utilized catalytic DABCO to perform the esterification of cinnamamide 99, where DABCO acted as a hydrogen-bond acceptor for phenol (Scheme 43B) [82]. Yuan-Yong and co-workers (2022) reported a DABCO/Fe3O4-catalyzed N-methyl amidation of cinnamic acid 122 via cooperation
Pd-Catalyzed asymmetric allylic amination with isatin using a P,olefin-type chiral ligand with C–N bond axial chirality
Beilstein J. Org. Chem. 2025, 21, 1018–1023, doi:10.3762/bjoc.21.83
- only approximately 1.3 days, also has a chiral induction ability. However, improvement is required in terms of the reactivity of the catalytic reaction. Subsequently, we investigated the effect of the base using (aR)-(−)-6 by testing various bases. The reaction in the presence of Na2CO3 delivered the
Recent total synthesis of natural products leveraging a strategy of enamide cyclization
Beilstein J. Org. Chem. 2025, 21, 999–1009, doi:10.3762/bjoc.21.81
- aldol condensation of 5 provided the tetracyclic α,β-unsaturated enone 6 in 57% yield. Subsequent catalytic hydrogenation using Pd/C conditions delivered the hydrogen to the alkene from the less hindered face, producing ketone 7 with high diastereoselectivity. Final reduction of both the amide and
- acetylcholinesterase (AChE) inhibitory activities [18]. In the presence of a catalytic amount of PPh3AuCl and AgSbF6, the enamide–alkyne cycloisomerization of bromo-substituted alkyne 8 proceeded via a 5-endo-dig cyclization to afford tricyclic compound 10 through the formation of iminium intermediate 9. The azepane
- , probably due to the formation of a more acidic cationic gold complex. Following this annulation, reduction of the amide in 20, catalytic hydrogenation of the alkene and the N-benzyl group, and subsequent nitrogen acylation yielded chloride 21 in a 42% total yield, setting the stage for the Witkop
Studies on the syntheses of β-carboline alkaloids brevicarine and brevicolline
Beilstein J. Org. Chem. 2025, 21, 955–963, doi:10.3762/bjoc.21.79
- achieved by a few-step transformation starting from brevicolline ((S)-1) isolated from natural sources (Scheme 2) [19]. When heating (S)-1 in benzoyl chloride, opening of the pyrrolidine ring and N-benzoylation occurred, resulting in compound 9. Debenzoylation of the latter to 10, followed by the catalytic
- debenzylated to brevicarine (2), isolated as a dihydrochloride salt. Müller et al. accomplished an alternative synthesis of brevicarine (2, Scheme 4) [23]. Compound 21 was obtained by treatment of nitrovinylindole 19 with N-methylpyrrole (20). Catalytic hydrogenation of the pyrrole ring and the nitro group of
- 21 under extremely harsh conditions (100 °C, 130 bar), followed by N-acetylation gave a mixture of diastereomeric racemates 22, which was cyclized to a diastereomeric mixture of β-carboline derivatives 23. Heating of 23 in pivalic acid in the presence of a catalytic amount of trifluoroacetic acid
Silver(I) triflate-catalyzed post-Ugi synthesis of pyrazolodiazepines
Beilstein J. Org. Chem. 2025, 21, 915–925, doi:10.3762/bjoc.21.74
- 13). Catalytic systems based on other transition metals including Cu(OTf)2 and the AuPPh3Cl/AgOTf combination were also tested (Table 1, entries 14 and 15). However, their performance was significantly poorer compared to AgOTf. To evaluate the scope and limitations of the optimized protocol (Table 1
Recent advances in controllable/divergent synthesis
Beilstein J. Org. Chem. 2025, 21, 890–914, doi:10.3762/bjoc.21.73
- , thereby offering unprecedented control over chemo-, regio-, and stereoselectivity parameters in catalytic manifolds. In 2015, the Jiang group developed a palladium-catalyzed regioselective three-component C1 insertion reaction (Scheme 1) [19]. In this reaction, an o-iodoaniline 1, phenylacetylene, and
- in steering catalytic selectivity. In 2016, the Jiang group achieved regioselective control in the gold-catalyzed intramolecular hydroarylation of alkynes by modulating the electronic and steric effects of ligands (Scheme 2) [20]. Mechanistically, the electron-deficient phosphite ligand L1 and the
- hydrogen atom transfer (HAT)/chiral copper dual catalytic system that achieved regiodivergent and enantioselective C(sp3)–C(sp3) and C(sp3)–N oxidative cross-couplings between N-arylglycine ester/amide derivatives and abundant hydrocarbon C(sp3)–H feedstocks (Scheme 6) [24]. This methodology also
Cu–Bpin-mediated dimerization of 4,4-dichloro-2-butenoic acid derivatives enables the synthesis of densely functionalized cyclopropanes
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
- reaction in the presence of MeOH in order to trap the potential copper intermediate by protonation. When 2 equiv of MeOH were used, we still obtained the dimerization product 2. Nevertheless, when a catalytic amount of base was used, we only observed the formation of β-borylation product 12 (Scheme 3b
Chitosan-supported CuI-catalyzed cascade reaction of 2-halobenzoic acids and amidines for the synthesis of quinazolinones
Beilstein J. Org. Chem. 2025, 21, 839–844, doi:10.3762/bjoc.21.67
- catalytic efficiency (up to 99% yield). Keywords: chitosan-supported CuI catalyst; cyclization reaction; mild conditions; quinazolinone; Introduction Quinazolinones are not only a key core of nitrogen-containing benzo heterocyclic compounds found in many natural products and bioactive molecules [1][2][3
- 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
- nonprotonated solvents such as THF and toluene were used, the yields were relatively low (Table 1, entries 1 and 2, 39 and 27% yields), indicating poor catalytic activity in these solvents. In contrast, using proton solvents (MeOH, iPrOH and H2O) led to improved yields (Table 1, entries 3−5, 51−60% yields
Synthesis and photoinduced switching properties of C7-heteroatom containing push–pull norbornadiene derivatives
Beilstein J. Org. Chem. 2025, 21, 807–816, doi:10.3762/bjoc.21.64
- catalytic back-conversion studies. Keywords: heterocycles; molecular solar thermal systems; norbornadiene; photochemistry; quadricyclane; Introduction In recent decades, the demand for renewable energy has increased tremendously [1]. A promising alternative to fossil fuels is the utilization of so-called
Regioselective formal hydrocyanation of allenes: synthesis of β,γ-unsaturated nitriles with α-all-carbon quaternary centers
Beilstein J. Org. Chem. 2025, 21, 800–806, doi:10.3762/bjoc.21.63
- catalytic hydrocyanation of alkenes [22], including the industrially relevant DuPont adiponitrile process from 1,3-butadiene using nickel catalysts [23], the hydrocyanation of allenes to produce functionalized β,γ-unsaturated nitriles with quaternary carbon centers has not been investigated extensively [24
Recent advances in the electrochemical synthesis of organophosphorus compounds
Beilstein J. Org. Chem. 2025, 21, 770–797, doi:10.3762/bjoc.21.61
- recent years. Recently, an electrochemical reaction of 2-isocyanobiaryls with diphenylphosphine oxides has been reported by Li et al. [45] using a Mn catalytic system with C(anode)/Pt(cathode) in an undivided cell. Different products were obtained with up to 85% yield in a constant flow for three hours
- carried out in a divided cell using platinum electrodes as the anode and cathode in the presence of pyridine as a base and ligand (Scheme 14). The catalyst behavior of palladium is attributed to its ability to form palladium clusters of specific sizes that exhibit high catalytic activity. However, this
- and copper foam (CF) as a cathode at a constant current of 14 mA. Experiments confirmed that the trace amount of copper dissolved from the cathode had no catalytic effect on the reaction. The reaction proceeded via anodic oxidation of diphenylphosphine followed by a reaction with alkenes to give
New advances in asymmetric organocatalysis II
Beilstein J. Org. Chem. 2025, 21, 766–769, doi:10.3762/bjoc.21.60
- 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
- organocatalytic cycloaddition reactions of unsaturated imines. A broad variety of activation modes, as well as catalyst structures, was covered and found to be useful in affording a diverse array of chiral N-heterocycles [27]. In my group, we recently became interested in atroposelective catalytic syntheses
Development and mechanistic studies of calcium–BINOL phosphate-catalyzed hydrocyanation of hydrazones
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
- . Trimethylsilyl cyanide (TMSCN) has been used as a sacrificial cyanide source. We found that isocyanide (rather than cyanide) is a preferred coordination to calcium during the catalytic cycle, while the active catalyst prefers a side-on coordination of cyanide. The configuration-determining step is a
- ; hydrazones; isocyanides; Introduction Catalytic applications of non-toxic earth abundant metals like calcium are currently on the rise [1][2][3][4]. Prominent recent examples that witness the versatility of calcium catalysis include calcium-catalyzed amination of π-activated alcohols [5], the Beckmann
Copper-catalyzed domino cyclization of anilines and cyclobutanone oxime: a scalable and versatile route to spirotetrahydroquinoline derivatives
Beilstein J. Org. Chem. 2025, 21, 749–754, doi:10.3762/bjoc.21.58
- conditions were optimized for the effective formation of tetrahydroquinoline derivatives with varying substituents, showing high yields under mild conditions. Mechanistic studies suggest a catalytic cycle involving nucleophilic attack by the aniline on the cyclobutanone oxime, followed by cyclization to form
- employ catalytic cyclization [9][10][11][12][13], reductive aminations [14][15][16][17], and photochemical cyclization [18][19][20]. However, these approaches often necessitate multistep syntheses of starting materials and involve intricate experimental procedures, significantly impeding their practical
- group tolerance. The optimized reaction conditions, utilizing copper(II) trifluoroacetate as the catalyst and hexane as the solvent, enabled the synthesis of the target products in good to excellent yields. Mechanistic studies suggest a catalytic cycle involving the formation of imine and enamine
Origami with small molecules: exploiting the C–F bond as a conformational tool
Beilstein J. Org. Chem. 2025, 21, 680–716, doi:10.3762/bjoc.21.54
- enzyme, and the hydroxy group of 57 interacts with catalytic aspartate residues in the active site. The fluorinated pepstatin analogue 58 was predicted to be pre-organised into the bent conformation and hence be a more potent inhibitor than 57. Compound 58 was indeed found to be more potent than 57
Photochemically assisted synthesis of phenacenes fluorinated at the terminal benzene rings and their electronic spectra
Beilstein J. Org. Chem. 2025, 21, 670–679, doi:10.3762/bjoc.21.53
- catalytic amount of I2 under an aerated condition. After the photolysis, the acetal moiety was partly cleaved to produce a mixture of acetal 9 and aldehyde 10. The obtained reaction mixture was treated with TsOH in acetone to afford desired fluorinated phenanthrenecarbaldehyde 10 in moderate yield (46% from
- common organic solvents. Therefore, the crude 18 was subjected to the Mallory photoreaction without purification. Photoirradiation of diarylethene 18 was performed in the presence of a catalytic amount of I2 in refluxing toluene to afford F87PHEN which was isolated by sublimation under vacuum. Absorption
Recent advances in allylation of chiral secondary alkylcopper species
Beilstein J. Org. Chem. 2025, 21, 639–658, doi:10.3762/bjoc.21.51
- low configurational stability of the chiral secondary organometallic 9 and organocopper species 10 [38]. Therefore, the development of a more broadly applicable catalytic system that could accomplish copper-catalyzed stereoselective allylic alkylation with chiral secondary nucleophiles represents a
- advancement requires establishing catalytic systems that effectively utilize chiral secondary organocopper species, making the understanding of their nature and behavior crucial for expanding the synthetic utility of this transformation. The purpose of this review is to present recent procedures for
- configurationally stable organoboron compounds was recently developed by Morken and co-workers, which employs only catalytic amounts of copper [47][48]. Their strategy uses chiral secondary organoboron compounds 20 as precursors to generate chiral alkylcopper species through a carefully controlled activation and
Photocatalyzed elaboration of antibody-based bioconjugates
Beilstein J. Org. Chem. 2025, 21, 616–629, doi:10.3762/bjoc.21.49
- ; ALFRED PASIEKA/SCIENCE PHOTO LIBRARY, No. 585105259. This content is not subject to CC BY 4.0. a. Photoredox catalytic cycles; b. absorption spectrum of photosensitizers. Therapeutic window indicates the most appropriate wavelength range to apply irradiation for biological applications. Graph
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