Approaches to stereoselective 1,1'-glycosylation

• Daniele Zucchetta and
• Alla Zamyatina

Beilstein J. Org. Chem. 2025, 21, 1700–1718, doi:10.3762/bjoc.21.133

• synthesis of neotrehalosamines related to the sugar moiety of the nucleoside antibiotic tunicamycin was performed using benzoylated 2-(benzoyloxyimino)-protected GlcN bromide donor 5, which enabled 1,2-cis stereochemical control through the non-participating C-2 benzoyloxyimino group, leading to the

• formation of an α-glycoside on the donor side [54]. On the acceptor side, the β-configuration was favored due to steric hindrance from the C-2 phthalimido group in the triacetylated GalN-lactol acceptors 6 or 3,4-di-O-benzylated acceptors 8, resulting in kinetically controlled formation of β,α-1,1

• diminish the reactivity of N-Troc-protected GlcN-derived donors [72]. Indeed, the presence of an electron-withdrawing group at position 3 of the GlcN-derived donor 70 merely required an elevated reaction temperature (0 °C), in contrast to the conditions used for the 3-O-Nap-protected GalN-based donor 68

Continuous-flow-enabled intensification in nitration processes: a review of technological developments and practical applications over the past decade

• Feng Zhou,
• Chuansong Duanmu,
• Yanxing Li,
• Jin Li,
• Haiqing Xu,
• Pan Wang and
• Kai Zhu

Beilstein J. Org. Chem. 2025, 21, 1678–1699, doi:10.3762/bjoc.21.132

• higher kinetic feasibility than aliphatic C-nitration in saturated carbon frameworks [3]. Following determination of substrate–nitrating agent combinations, reactor system specification emerges as the critical engineering decision. Nitration reactor selection – encompassing batch, semi-batch, continuous

• selective mono- or di-nitration and facilitates late-stage C–H nitration of biorelevant molecules, with DFT/mechanistic studies revealing synergistic 'nitro effect' and 'methyl effect' underlying the reactivity [7]. Jia et al. developed dinitro-5,5-dimethylhydantoin (DNDMH) as an efficient arene nitration

• frequently exhibit significant flow rate deviations between programmed and actual delivery rates under high-flow conditions. This flow instability can be mitigated through a strategic thermal management of reagents (30–60 °C) or implementing back-pressure regulation (0.5–2 bar) via inert gas pressurization

Structural analysis of stereoselective galactose pyruvylation toward the synthesis of bacterial capsular polysaccharides

• Tsun-Yi Chiang,
• Mei-Huei Lin,
• Chun-Wei Chang,
• Jinq-Chyi Lee and
• Cheng-Chung Wang

Beilstein J. Org. Chem. 2025, 21, 1671–1677, doi:10.3762/bjoc.21.131

• a = 16.1017(4) Å, b = 7.7608(2) Å, c = 28.8344(8) Å, and β = 93.3680(10)°. Additionally, the presence of lattice water greatly influenced the molecular packing. The hydrogen bond (H–O–H) lengths in this lattice water ranged from 1.923 to 2.204 Å (Figure 2b). The pyruvylated galactose 6 was utilized

• position. Additionally, THF was used as a solvent to enhance the α-selectivity of the reaction [41][42][43]. Next, while both compounds 8 and 9 can act as acceptors, compound 9, a primary alcohol, exhibits greater nucleophilicity. Using the TolSCl/AgOTf promoter system at −70 °C, the β-linked disaccharide

Influence of the cation in hypophosphite-mediated catalyst-free reductive amination

• Natalia Lebedeva,
• Fedor Kliuev,
• Olesya Zvereva,
• Klim Biriukov,
• Evgeniya Podyacheva,
• Maria Godovikova,
• Oleg I. Afanasyev and
• Denis Chusov

Beilstein J. Org. Chem. 2025, 21, 1661–1670, doi:10.3762/bjoc.21.130

• an important role in medicinal and pharmaceutical chemistry [23][24][25] (Scheme 1a). Sodium hypophosphite exhibited good chemoselectivity – it selectively reduced imines while leaving other functional groups intact, e.g., nitro (NO₂), cyano (CN), alkene (C=C), and benzyloxy (OBn) groups. In contrast

• , usage of classical reducing agents – H2 on Pd/C or NaBH4 did not show similar chemoselectivity [26]. Additionally, the NaH2PO2 usability is engaging due to fine green chemistry metrics, e.g., an E-factor less than 1 was reached, moreover the main wastes of this process were safe and useful as

• synthesis of esters of phosphonous or alkylphosphinic acids [33][34][35]. Only a single application of cesium hypophosphite was shown in the literature. CsH2PO2 was prepared in situ and used for formation C–P bond by radical addition to unsaturated carboxylic acids [36 ]To summarize the above, it is crucial

Catalytic asymmetric reactions of isocyanides for constructing non-central chirality

• Jia-Yu Liao

Beilstein J. Org. Chem. 2025, 21, 1648–1660, doi:10.3762/bjoc.21.129

• and manifests in diverse forms (Figure 1a). While central chirality based on stereogenic centers (e.g., C, P, S, etc.) is the most conventional type, non-central chirality, such as axial [1][2][3][4], planar [5][6][7], helical [8][9][10], and inherent chirality [11][12], has gained increasing

• iodides (Scheme 1a) [27]. This transformation proceeded via two key steps, isocyanide insertion and desymmetric C(sp2)–H bond activation. By using phosphoramidite L1 as the chiral ligand, planar chiral pyridoferrocenes 2 were obtained in 61–99% yield with 72–99% ee. In addition, this catalytic system

• ) and aryl iodide 6a as the reactants, diastereomeric products 9a and 9b, each containing two distinct stereogenic axes (C–C and C–N), were obtained in 93% and 89% ee, respectively. Very recently, Luo and co-workers implemented an efficient palladium-catalyzed atroposelective C(sp2)–H imidoylative

Formal synthesis of a selective estrogen receptor modulator with tetrahydrofluorenone structure using [3 + 2 + 1] cycloaddition of yne-vinylcyclopropanes and CO

• Jing Zhang,
• Guanyu Zhang,
• Hongxi Bai and
• Zhi-Xiang Yu

Beilstein J. Org. Chem. 2025, 21, 1639–1644, doi:10.3762/bjoc.21.127

• annulation to construct the C ring (cyclohexenone ring), and an intramolecular SN2 reaction to build the D ring (five-membered ring) [15][16][17][18]. In 2013, Wallace and co-workers disclosed the second route for this molecule (Scheme 2B) [19], in which the five-membered ring B was formed by utilizing

• not known). A hydrogenation reaction to reduce the C=C bond in 11 was then successfully applied, delivering product 12 in 80% yield (5 mol % RhCl(PPh3)3 catalyst and 1 atm hydrogen atmosphere were used). Next, we tested whether Krapcho decarboxylation reaction can convert 12 into 1 in one step

On the aromaticity and photophysics of 1-arylbenzo[a]imidazo[5,1,2-cd]indolizines as bicolor fluorescent molecules for barium tagging in the study of double-beta decay of ¹³⁶Xe

• Eric Iván Velazco-Cabral,
• Fernando Auria-Luna,
• Juan Molina-Canteras,
• Miguel A. Vázquez,
• Iván Rivilla and
• Fernando P. Cossío

Beilstein J. Org. Chem. 2025, 21, 1627–1638, doi:10.3762/bjoc.21.126

• -phenylene moiety in the tetracyclic structure. Combination of reactions A and B in the form yields an average value of ⟨ΔEAB⟩ = −22.6 kcal/mol. A similar treatment of the separate components as outlined in reactions C and D shows a much lower stabilization energy for imidazo[1,2-a]pyridine 8 and a higher

• optimal CC or CN distances associated with aromatic structures, represents the corresponding bond distance gathered in Figure 3B, and αk is a parametric term defined as where is the standard single bond distance of the k-pair of atoms (C–C, C–N) and is the same paremeter but referred to the

• corresponding double bonds (C=C, C=N). We computed the HOMA values associated with the total, peripheral and modular patterns using the standard parameters and a more recent set based on computational parameters that take into account antiaromaticity, denoted as HOMAc [23]. According to our results, formal

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

• deformed reactants along the reaction coordinate, defined in this case by the shortest C···C bond-forming distance. From the data in Figure 2a, which shows the computed activation strain diagrams (ASDs) for the uncatalyzed and AlCl3-catalyzed reactions from the beginning of the process up to the respective

• repulsion between the deformed reactants (Figure 2b). The less destabilizing Pauli repulsion computed for the catalyzed cycloaddition directly originates from the reduction of the electron density at the reactive C–C double bond of the dienophile, which translates into a lower <π(diene)|π(dienophile

• )> molecular orbital overlap (S = 0.13 vs S = 0.07 for the uncatalyzed and catalyzed reactions, respectively). In other words, there occurs a significant polarization of the conjugated π-system away from the C–C double bond when the LA binds the carbonylic oxygen of methyl acrylate, which results in a less

Synthesis of optically active folded cyclic dimers and trimers

• Ena Kumamoto,
• Kana Ogawa,
• Kazunori Okamoto and
• Yasuhiro Morisaki

Beilstein J. Org. Chem. 2025, 21, 1603–1612, doi:10.3762/bjoc.21.124

• lifetime measurement was performed on a Hamamatsu Photonics Quantaurus-Tau fluorescence lifetime spectrometer system. Specific rotations ([α]Dt) were measured with a HORIBA SEPA-500 polarimeter: concentration “c” is g/dL. Circular dichroism (CD) spectra were recorded on a JASCO J-1500 spectropolarimeter

• , 93.81, 95.72, 105.99, 125.16, 125.33, 125.42, 125.91, 128.07, 128.27, 131.99, 133.24, 134.65, 135.30, 141.30, 142.58 ppm: HRMS (APCI+) (m/z): [M + H]+ calcd. for C56H62Si2, 791.4463; found, 791.4472; [α]D25 –203.25 (c 0.04, CHCH3). (Rp)-3 was obtained by the same procedure of (Sp)-3. HRMS (APCI+) (m/z

• ): [M + H]+ calcd. for C56H62Si2, 791.4463; found, 791.4442; [α]D25 = +199.73 (c 0.04, CHCH3). Synthesis of (Sp)-4 (Sp)-3 (43.0 mg, 0.054 mmol) was dissolved in THF (2 mL), followed by the addition of Bu4NF (1.0 M in THF solution, 0.11 mL). The reaction was carried out at room temperature for 30 min

3-Aryl-2H-azirines as annulation reagents in the Ni(II)-catalyzed synthesis of 1H-benzo[4,5]thieno[3,2-b]pyrroles

• Julia I. Pavlenko,
• Pavel A. Sakharov,
• Anastasiya V. Agafonova,
• Derenik A. Isadzhanyan,
• Alexander F. Khlebnikov and
• Mikhail S. Novikov

Beilstein J. Org. Chem. 2025, 21, 1595–1602, doi:10.3762/bjoc.21.123

• method for the synthesis of 3-arylbenzo[4,5]thieno[3,2-b]pyrroles has been developed via pyrrole ring annulation to the aromatic benzo[b]thiophene system, using 3-arylazirines as a N‒C=C synthon. The reaction is catalyzed by Ni(hfacac)2 and proceeds through the azirine ring opening across the N=C3 bond

• unique ability of these compounds to undergo selective opening of the three-membered ring at either of the two nitrogen–carbon bonds under certain conditions and to be incorporated into the target molecule as a N‒C‒C synthon is successfully used to obtain a variety of heterocyclic and acyclic nitrogen

• -dicarbonyl tautomeric form. Initially, it was shown that compound 1 does not react with 3-(p-tolyl)-2H-azirine (2a) when heated at 100 °C in methanol (Table 1, entry 1). No reaction was observed either in the presence of Rh(I), Mn(III), Fe(II), and Cu(II) compounds (Table 1, entries 2‒5). The Cu(I) compounds

Chemical synthesis of glycan motifs from the antitumor agent PI-88 through an orthogonal one-pot glycosylation strategy

• Shaokang Yang,
• Xingchun Sun,
• Hanyingzi Fan and
• Guozhi Xiao

Beilstein J. Org. Chem. 2025, 21, 1587–1594, doi:10.3762/bjoc.21.122

• in mannosyl PVB 8 (1.0 equiv) in the presence of TMSOTf as catalyst proceeded smoothly at 0 °C to room temperature, affording the α-Man-(1→3)-Man PVB disaccharide. The further coupling of the above PVB disaccharide with the poorly reactive 2-OH in mannoside 9 (0.9 equiv) under activation with NIS and

• TMSOTf at 0 °C to room temperature, successfully furnished the desired α-Man-(1→3)-α-Man-(1→3)-α-Man trisaccharide 10 in 87% yield in a one pot manner. Removal of TBDPS group in 10 with 70% HF·pyridine and subsequent phosphitylation of the resulting free alcohol with phosphoramidite 11 provided the

• desired phosphite, which was further oxidized by 3-chloroperoxybenzoic aicd (mCPBA) at −78 °C to 0 °C, producing the desired phosphorylated fully protected trisaccharide 12 in 79% overall yield over three steps. Removal of all protecting groups in trisaccharide 12 is a challenging task due to the presence

Thermodynamic equilibrium between locally excited and charge transfer states in perylene–phenothiazine dyads

• Issei Fukunaga,
• Shunsuke Kobashi,
• Yuki Nagai,
• Hiroki Horita,
• Hiromitsu Maeda and
• Yoichi Kobayashi

Beilstein J. Org. Chem. 2025, 21, 1577–1586, doi:10.3762/bjoc.21.121

• ). (c) Simulated absorption spectra of these compounds (B3LYP/6-31+G(d,p)//B3LYP/6-31+G(d,p) level of theory), and (d) molecular orbitals mainly contributing to the optical transitions indicated by arrows. Emission decay curves of Pe–PTZ(TPA)2 in benzene excited at 403 nm and probed at 460 and 632 nm

• (a, c) 350 nm (20 nJ/pulse) and (b, d) 420 nm (6 nJ/pulse) at room temperature. (a) Femtosecond-to-nanosecond transient absorption spectra and (b) evolution-associated spectra (EAS) of Pe–Ph–PTZ(TPA)2 in benzene excited at 350 nm (20 nJ/pulse) at room temperature. Summarized photophysical process of

pH-Controlled isomerization kinetics of ortho-disubstituted benzamidines: E/Z isomerism and axial chirality

• Ryota Kimura,
• Satoshi Ichikawa and
• Akira Katsuyama

Beilstein J. Org. Chem. 2025, 21, 1568–1576, doi:10.3762/bjoc.21.120

• advances require expanding the range of pH-responsive systems and discovering new molecular architectures. Here, we investigate the pH-responsive behavior of ortho-disubstituted benzamidine, which generates atropisomers and E/Z isomers. The amidine moiety allows modulation of the C–N and C–N/C–C rotational

• barriers by protonation, providing a novel approach to control the kinetics of isomerization via pH adjustment. The results showed that protonation of the amidine moiety significantly suppresses both C–N bond rotation and C–N/C–C concerted rotation, demonstrating the potential of ortho-disubstituted

• switches [19]. For example, hydrazone-based molecular switches undergo reversible E/Z isomerization around the C=N bond [1][2][3][4][5][6][7], with protonation significantly shifting the equilibrium. Beyond double-bond isomerization, pH stimuli have also been employed to modulate rotational barriers in

Synthesis of an aza[5]helicene-incorporated macrocyclic heteroarene via oxidation of an o-phenylene-pyrrole-thiophene icosamer

• Yusuke Matsuo,
• Aoi Nakagawa,
• Shu Seki and
• Takayuki Tanaka

Beilstein J. Org. Chem. 2025, 21, 1561–1567, doi:10.3762/bjoc.21.119

• , respectively [19][20]. Recently, our group established an efficient synthetic strategy for strained macrocyclic polyarenes, such as compound C, in which o-phenylene units preorganize adjacent heteroaromatics into close proximity, thereby facilitating oxidative ring-closure reactions [21]. Among these, the

• macrocycle whose structure has been confirmed by X-ray diffraction analysis. Next, oxidation of 4 was attempted using [bis(trifluoroacetoxy)iodo]benzene (PIFA) in CH2Cl2 at −78 °C (Scheme 2). These reaction conditions had previously proven effective for the oxidation of 3 and other o-phenylene-bridged

• acyclic heteroaromatics [26][27]. Thus, to a solution of 4 in CH2Cl2 was added 15 equivalents of PIFA at −78 °C and stirred for 3 h. The mixture was then allowed to warm to room temperature to give a dark solution. The system was worked-up with NaBH4/MeOH for 10 minutes followed by extraction with CH2Cl2

Facile synthesis of hydantoin/1,2,4-oxadiazoline spiro-compounds via 1,3-dipolar cycloaddition of nitrile oxides to 5-iminohydantoins

• Juliana V. Petrova,
• Varvara T. Tkachenko,
• Victor A. Tafeenko,
• Anna S. Pestretsova,
• Vadim S. Pokrovsky,
• Maxim E. Kukushkin and
• Elena K. Beloglazkina

Beilstein J. Org. Chem. 2025, 21, 1552–1560, doi:10.3762/bjoc.21.118

• Federation, 115478, Moscow, Russian Federation 10.3762/bjoc.21.118 Abstract The cycloaddition of 1,3-dipoles at C=N bonds is a relatively rare process, in contrast to the widespread cycloaddition reactions at C=C, C≡C, and C=S bonds. In this study, we present the syntheses of novel hydantoin/1,2,4

• -oxadiazoline spiro-compounds using a 1,3-dipolar cycloaddition of nitrile oxides to C=N bonds of 5-iminohydantoins. The efficiency of the approach was demonstrated by varying the substituents at four positions of the resulting spirocyclic molecules. Cytotoxicity of the target hydantoin/1,2,4-oxadiazolines was

• of double and triple bonds, most of the described reactions are related to dipolarophiles with C=C, C≡C or C=S bonds [7]. However, the [3 + 2]-cycloaddition of nitrile oxides to exocyclic C=N bonds, is a much less explored area. There are few known reactions of these dipoles with imino derivatives of

Azide–alkyne cycloaddition (click) reaction in biomass-derived solvent Cyrene^TM under one-pot conditions

• Zoltán Medgyesi and
• László T. Mika

Beilstein J. Org. Chem. 2025, 21, 1544–1551, doi:10.3762/bjoc.21.117

• it is negative in the Ames test [25]. Recently, we determined key physicochemical properties of CyreneTM and showed that it has a negligible vapor pressure (<9.6 kPa) and low viscosity (<6.8 mPa·s) at typical transition-metal-catalyzed reaction temperatures (30–140 °C) [26]. CyreneTM has been

• , a wide range of organic reactions, e.g., urea and amide formation [32][33], amide coupling [34], aldol condensation [35], C–H difluoromethylation [36], aromatic substitution [37], and MOFs synthesis [38] were demonstrated in CyreneTM. Very recently, Fasano and Citarella first reported a CuAAC

• ) were tested in the conversion of 1.15 mmol benzyl azide (1a) and 1 mmol phenylacetylene (2a) in 2.5 mL CyreneTM at 30 °C. All the selected Cu salts catalyzed the cycloaddition; however, Cu chlorides and oxides resulted in unexpectedly low product yields after 0.5 h. The solubility of Cu oxides was

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

• -dimethylformamide (DMF) at 20 °C afforded the best results, giving the desired product 9a in 70% isolated yield (Table 1, entry 1). Changing NiBr2·diglyme to other nickel salts, such as Ni(OTf)2 and NiCl2·diglyme led to lower yields (Table 1, entries 2 and 3). Similarly, changing the ligand for dtbbpy or

• . Simultaneously, acridinium photocatalyst PC1 absorbed energy and transitioned from the ground state to excited state under visible-light irradiation. This excited state PC1* is quenched by the amine, generating the amine radical cation and PC1 radical via a single-electron transfer (SET) process. Then, the C−Br

• bond of I is cleaved by PC1•, generating a C-centered radical II, which can be further reduced to give an enolate III, that ultimately evolves to the more stable anion IV and undergoes protonation to afford the final enaminone product 9a. Conclusion In summary, a simple and effective nickel-assisted

Azobenzene protonation as a tool for temperature sensing

• Antti Siiskonen,
• Sami Vesamäki and
• Arri Priimagi

Beilstein J. Org. Chem. 2025, 21, 1528–1534, doi:10.3762/bjoc.21.115

• is assumed. Stronger electron donation gives rise to larger red-shift, and hence more pronounced color changes, upon protonation, as illustrated in Figure 1C. Figure 1D illustrates the shift in protonation equilibrium with increasing acidity when MSA is added to DCE solution of 3 at 25 °C. Due to the

• with 1.44 mM MSA over a 10–80 °C temperature range. Comparing the maximum absorbances at the neutral and protonated peaks provides a measure of sensitivity and optimal working range. Figure 2B presents this comparison for 1–3 in MSA/DCE solutions, calculated as the ratio between neutral and protonated

• , the rate of change should be both high and systematic. For example, in Figure 2B, the optimal range for 3 appears to be between 30 and 80 °C, where the rate of change is fastest and follows a clean, exponential trend. All three compounds show similar sensitivity in DCE, while the sensitivity of 3 is

Calcium waste as a catalyst in the transesterification for demanding esters: scalability perspective

• Anton N. Potorochenko and
• Konstantin S. Rodygin

Beilstein J. Org. Chem. 2025, 21, 1520–1527, doi:10.3762/bjoc.21.114

• acetylene production, was investigated. The catalyst was obtained by calcination of calcium carbide slag at 600 °C (CS600) and characterized by XRD and FTIR analysis. The transesterification reactions were carried out with primary alcohols, producing fatty acid alkyl esters in 51–99% yields, depending on

• was calcined at 600 °C before use and the catalyst CS600 was characterized using XRD and FTIR analysis, confirming the presence of CaO as the main phase. The primary alcohols successfully reacted in the transesterification reaction to give the corresponding fatty acid alkyl ester mixtures in yields

• fine organic synthesis. Results and Discussion The carbide slag was prepared by hydrolysis of commercially available calcium carbide (Sigma-Aldrich) and oven dried at 80 °C for 3 hours. The active catalyst CS600 was prepared by calcining the carbide slag at 600 °C for 2 hours. The composition of the

Ambident reactivity of enolizable 5-mercapto-1H-tetrazoles in trapping reactions with in situ-generated thiocarbonyl S-methanides derived from sterically crowded cycloaliphatic thioketones

• Grzegorz Mlostoń,
• Małgorzata Celeda,
• Marcin Palusiak,
• Heinz Heimgartner,
• Marta Denel-Bobrowska and
• Agnieszka B. Olejniczak

Beilstein J. Org. Chem. 2025, 21, 1508–1519, doi:10.3762/bjoc.21.113

• five-membered heterocycles via [3 + 2]-cycloaddition reactions. Depending on the type of the dipolarophile used in these reactions, the target heterocycles may contain only one sulfur atom (cycloadditions with C=C or C≡C dipolarophiles) or more heteroatoms (cycloadditions with C=S, C=O, C=N, N=N, S=O

• sulfur (χ = 2.55 (for C) and χ = 2.58 (for S) according to the Pauling scale), thiocarbonyl S-methanides 1 are considered as electron-rich 1,3-dipoles with basic and nucleophilic reactivity displayed by the =S+–CH2‒ unit [6]. Therefore, acidic compounds of type R–XH (X = NR’, O, S), which are able to

• ], were analogously treated with CH2N2 at ca. 0 °C and the expected cycloadducts 2c and 2d were formed with complete regioselectivity, and subsequently could be isolated in good yields without a remarkable decomposition (Scheme 3). Thermal decomposition of 2a and 2b, and the behavior of the corresponding

Highly distinguishable isomeric states of a tripodal arylazopyrazole derivative on graphite through electron/hole-induced switching at ambient conditions

• Himani Malik,
• Sudha Devi,
• Debapriya Gupta,
• Ankit Kumar Gaur,
• Sugumar Venkataramani and
• Thiruvancheril G. Gopakumar

Beilstein J. Org. Chem. 2025, 21, 1496–1507, doi:10.3762/bjoc.21.112

• intermediates. (c) All 8 states are accessible reversibly even at lower sample voltages, indicating that switching can be performed between any given state at a low threshold voltage. That is, all states are accessible and are remarkably stable at all sample voltages. It is concluded that the high energy

• pyrolytic graphite (HOPG, ZYB grade from μMasch). Approximately 4 μL of solutions of FNAAP were drop-casted on the HOPG surface, dried (a few minutes) in ambient conditions, and AFM/STM studies were performed. Relative humidity (≈50%) and temperature (22–25 °C) of the room were controlled by an air

• conditioner and a dehumidifier. While drop casting, the sample was kept at ≈20–30 °C to ensure a smooth flow of the solvent over the substrate. After drop casting, all films were subjected to vacuum pumping (typically 0.01 mbar) for about 1 h. Before depositing molecules, freshly cleaved graphite surfaces

Heterologous biosynthesis of cotylenol and concise synthesis of fusicoccane diterpenoids

• Ye Yuan,
• Zhenhua Guan,
• Xue-Jie Zhang,
• Nanyu Yao,
• Wenling Yuan,
• Yonghui Zhang,
• Ying Ye and
• Zheng Xiang

Beilstein J. Org. Chem. 2025, 21, 1489–1495, doi:10.3762/bjoc.21.111

• ][23][24][25][26]. Most of these synthetic approaches rely on similar strategies, i.e., coupling of the A ring and the C ring followed by the formation of the B ring. Additionally, the semisynthesis of analogues of 1 has been reported and led to the discovery of ISIR-050 (4), which shows higher

• activity than cotylenin A in cell growth inhibition assays and less toxicity in single-agent treatments [27][28]. Recently, Jiang and Renata described a chemoenzymatic approach that combines the skeletal construction by chemical methods and enzymatic C–H oxidations [29]. The synthesis employs a catalytic

• Nozaki–Hiyama–Kishi reaction and a one-pot Prins cyclization/transannular hydride transfer to construct the 5-8-5 tricyclic scaffold. Enzymatic oxidations were used to install the hydroxy group at the C-3 position. Ten fusicoccanes were synthesized in 8–13 steps each. Despite these efforts, a strategy

Copper catalysis: a constantly evolving field

• Elena Fernández and
• Jaesook Yun

Beilstein J. Org. Chem. 2025, 21, 1477–1479, doi:10.3762/bjoc.21.109

• straightforward reactions. Complementarily, the Review article by Jang and Kim provides a deep understanding of recent advances in the combination of electrochemistry and copper catalysis for various organic transformations [3]. Their contribution elaborates various C–H functionalizations, olefin additions

• , decarboxylative functionalizations, and Chan–Lam coupling reactions. In doing so, the authors point out the combination of transition-metal catalysis and electrochemistry as an efficient, sustainable method for the oftentimes challenging formation of C–C and C–heteroatom bonds in complex molecules. Another Review

• -workers demonstrates that the efficient and green direct C–H amination of benzoxazoles can be catalyzed by copper chloride salts in acetonitrile in the absence of any acidic, basic, or oxidizing additives [8]. Both CuCl and CuCl2 were found to be extremely efficient in promoting the reactions, which

Microwave-enhanced additive-free C–H amination of benzoxazoles catalysed by supported copper

• Andrei Paraschiv,
• Valentina Maruzzo,
• Filippo Pettazzi,
• Stefano Magliocco,
• Paolo Inaudi,
• Daria Brambilla,
• Gloria Berlier,
• Giancarlo Cravotto and
• Katia Martina

Beilstein J. Org. Chem. 2025, 21, 1462–1476, doi:10.3762/bjoc.21.108

• offers wide-ranging potential for substrate expansion and the functionalisation of bioactive compounds. This study presents a green and efficient C–H amination, catalysed by CuCl and CuCl2, in acetonitrile without acidic, basic or oxidant additives that is accelerated by microwave (MW) irradiation and is

• , and the huge overall economic impact of these processes. Inspired by the logic behind cross-dehydrogenative C–C-coupling methods [15], the direct C–H amination has been developed as a more straightforward, economical and environmentally friendly reaction, compared to its counterparts (such as the

• classical Buchwald–Hartwig amination reaction [16] or the Ullman reaction [17][18]) which require pre-functionalisation steps and harsh conditions [19]. Many protocols for C–H aminations have been applied to heteroaromatic compounds, mainly 5-membered heteroarenes, and a great deal of attention has been

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

• ruled out. The structures of compounds 3, 4, and 5 were determined by X-ray diffraction analysis (Figure 2). Mono-olefin 3 and bis-olefin 5 adopt a bathtub-like chiral macrocyclic structure rather than figure-eight conformation. Both compounds crystallize as a racemic pair of enantiomers with P21/c and

• low racemization barrier as with structurally similar methylenedioxy-substituted DBC derivative [22]. Racemization dynamics The racemization barriers of CBBC 1, mono-olefin 3, and bis-olefin 5 were evaluated by monitoring the decrease of circular dichroism (CD) signals in 1,2-dichlorobenzene at 170 °C

• conformation (Sa,Sa)-A is feasible with a small activation barrier of 9.9 kcal mol−1. The figure-eight conformer (M,M)-B untwists to adopt an achiral conformation C with the exo-alkene units rotated inwards in opposite directions. These conformational changes are almost identical to those of CBBC 1. However