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

• -31+G(d,p)//B3LYP/6-31+G(d,p) level of theory. Steady-state (a) absorption and (b) emission spectra of Pe–PTZ, Pe–PTZ(TPA), Pe–PTZ(TPA)2, and Pe–Ph–PTZ(TPA)2 in benzene at room temperature. The excitation wavelength was 420 nm for Pe–PTZ, Pe–PTZ(TPA)2, and Pe–Ph–PTZ(TPA)2, and 415 nm for Pe–PTZ(TPA

• . Microsecond transient absorption (a) spectra and (b) dynamics of Pe–PTZ(TPA)2 in benzene excited at 355 nm (5 μJ/pulse) and probed at 430 nm under nitrogen and oxygen conditions. Femtosecond-to-nanosecond transient absorption spectra and evolution-associated spectra (EAS) of Pe–PTZ(TPA)2 in benzene excited at

• (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

• substitution of an ortho-disubstituted benzamide (DiBA) increases the rotational barrier of the C–N and C–N/C–C concerted rotation (Figure 1a,b) [20]. The observation can be explained mainly by the double-bond nature of the chalcogen amide C–N bond, which is attributed to a zwitterionic resonance structure of

• various fields, such as functional materials, biological probes, and drugs. a) Structural features of DiBA. b) Resonance structure of the amide moiety of DiBA. c) Molecular form and protonated structure of ortho-disubstituted benzamidine. Rotational barriers of 2-bromo-N,N,6-trimethylbenzimidamide and its

• protonated form calculated by the DFT method. Comparison of VT-NMR spectra of a) amidine 1 and b) its trifluoroacetate salt 1-H+ in DMSO-d6 (400 MHz). Separation and isolation of amidine E/Z isomers by RP-HPLC. The mobile phase contained CF3CO2H to protonate the amidine moiety. Kinetic analysis of the

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

• ] and pyrenylenes [17][18] were reported to adopt unique chiral arrangements depending on their stereochemistry. Helical motifs such as carbo[4]helicene and oxa[5]helicene were incorporated into cyclic structures, giving rise to cyclic carbo[4]helicenylene A and cyclic oxa[5]helicenylene-biphenylene B

• and nanobelt. (b) Cyclo[4]helicenylene and cyclo(oxa[5]helicenylene-biphenylene). (c) Intramolecular oxidative coupling of cyclic o-phenylene-pyrrole-thiophene dodecamers. X-ray crystal structure of 4. Thermal ellipsoids are scaled to 50% probability level. Solvent molecules and hydrogen atoms except

• for NHs are omitted for clarity. 1H NMR spectra of 5 in DMSO-d6 (a) at room temperature and (b) at 100 °C. (a) X-ray crystal structure of 5; (left) top view, (right) side view. Thermal ellipsoids are scaled to 50% probability level. Solvent molecules and hydrogen atoms except for NHs are omitted for

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

• '-disubstituted ureas were initially reacted with oxalyl chloride to form imidazolidinetriones 1a,b, which were then added to an iminophosphorane formed in situ from an aryl azide and triphenylphosphine. As a result of the aza-Wittig reaction, 5-iminohydantoins 2a–i were then used as dipolarophiles in the 32CA

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

• ://www.chemcraft.org) and Avogadro version 1.2.0 (http://www.avogadro.cc). A) Protonation reaction scheme of azobenzene (1), 4-methoxyazobenzene (2), and 4,4'-dimethoxyazobenzene (3) with acid (HA). The parentheses indicate additional acid molecule(s) stabilizing the anion. B) Absorption spectra of 1, 2, and 3 in 1,2

• the degree of protonation of compound 3 (40 μM at 25 °C) in DCE with 1.44 mM MSA added. The reference spectra of 3 in pure DCE and pure MSA have been calculated for 40 µM solutions from molar absorption coefficients. B) Ratio of neutral and protonated π → π* absorption peak maxima for compounds 1–3 at

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

• organic synthetic reactions. XRD pattern of CS600. CS600 reusability test. Reaction conditions: 2 wt % CS600, MeOH/4a ratio is 12:1, 65 °C, 4 h. XRD patterns of the CS600 catalyst after the 1st reaction cycle: A) after washing with methanol and hexane and drying at 80 °C for 30 min; B) after calcination

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

• Grzegorz Mloston Malgorzata Celeda Marcin Palusiak Heinz Heimgartner Marta Denel-Bobrowska Agnieszka B. Olejniczak Department of Organic and Applied Chemistry, Faculty of Chemistry, University of Lodz, Tamka 12, 91-403 Łódź, Poland Department of Physical Chemistry, Faculty of Chemistry, University

• structure of the N-insertion product (thioaminal) 9i. Atoms are represented by thermal ellipsoids (50%). For graphics with atoms labelling see Figure S22(a) (Supporting Information File 1); (b) molecular structure of the S-insertion product (dithioacetal) 10i. Atoms are represented by thermal ellipsoids (50

• %). For graphics with atoms labelling see Figure S22(b) in Supporting Information File 1. Typical [3 + 2] cycloaddition (above) and trapping (below) reactions of thiocarbonyl S-methanides 1a and 1b derived from cycloaliphatic thiones (adamantanethione (7a) and 3-thioxo-2,2,4,4-tetramethylcyclobutanone (7b

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

• Supporting Information File 1. The AFM images of the ultra-thin film reveal domains of assembled molecules shown as bright contrast, marked by green and yellow dashed lines in Figure 2a,b. The pristine graphite surface has a median contrast. The molecular domains are growing as long islands with well-defined

• graphite lattice, which has 3-fold symmetry [33][34][35]. Each of the orientations has a mirror domain as well, making a total of six orientations for the islands on the surface. The orientations of the islands are marked by yellow and green 3-fold arrowheads in Figure 2a,b. The mirror orientations are

• originating from a hexagonal type of lattice. To further understand the microscopic structure of the assembly, we have performed STM experiments on ultra-thin films of FNAAP. Figure 3a,b shows constant current STM topographs of ultra-thin films of an FNAAP adlayer on HOPG (0001) at different resolutions

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

• chemical steps. This work lays the foundation for the preparation of fusicoccane natural products and exploration of their biological activities. Selected fusicoccane diterpenoids and overview of this study. (a) Representative members of the fusicoccane diterpenoid family. (b) This work: heterologous

• biosynthesis of cotylenol (3) in an engineered Aspergillus oryzae strain and concise synthesis of fusicoccane diterpenoids. Heterologous production of brassicicene I in an engineered A. oryzae strain. (a) Biosynthesis of fusicoccin A in Phomopsis (Fusicoccum) amygdali. (b) Brassicicene BGC in A. brassicicola

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

• changes in the position and shape of the νNH2 and δNH2 bands are observed, which are an indirect indication of the interaction of the amino group with the metal (curve b) [51]. On the other hand, major changes are observed in the spectrum of 5 wt % Si –MonoAm-Cu(II) (curve d). These are particularly

• comparing the corresponding FESEM images of the fresh and used catalyst (see Figure 7a and b). EDS maps show a homogeneous dispersion of copper on the catalyst with this dispersion being maintained after the catalysts is used (panels a and b of Figure 8). Conclusion The study demonstrates that the efficient

• the reaction started, the reactor was pressurized with 5 bar of air (for experimental MW setup see Supporting Information File 1). Reaction of benzimidazole with piperidine. a) Reaction scheme including intermaidates and b) conversion and selectivity plot of the C2-amination of benzoxazole with

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

• stable figure-eight conformation A to a metastable bathtub conformation B with a small energy difference of approximately 2 kcal mol–1 [21]. In this paper, we discuss the effect of the transformation of the carbonyl groups on the conformational change of the figure-eight structure. We thus intentionally

• . The racemization dynamics of 5 was investigated by DFT calculations at the B3LYP/6-31G(d) level of theory, employing the Gaussian 16 software package and the global reaction route mapping (GRRM17) [23] program (Figure 4). The interconversion between figure-eight conformation (M,M)-B and bathtub

• 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

Advances in nitrogen-containing helicenes: synthesis, chiroptical properties, and optoelectronic applications

• Meng Qiu,
• Jing Du,
• Nai-Te Yao,
• Xin-Yue Wang and
• Han-Yuan Gong

Beilstein J. Org. Chem. 2025, 21, 1422–1453, doi:10.3762/bjoc.21.106

• helical architectures, have attracted considerable attention due to their intrinsic chirality and tunable optoelectronic properties. Among them, nitrogen-doped helicenes (azahelicenes) and their heteroatom-co-doped counterparts – such as B/N-, O/N-, S/N-, and Se/N-doped helicenes – have emerged as highly

• helicenes. Particular attention is given to multi-heteroatom systems co-doped with elements such as boron, oxygen, sulfur, and selenium, highlighting their influence on CPL performance and structure–property relationships. We classify the nitrogen-doped helicenes into only N-containing helicenes, B,N

• , thereby advancing their application in multifunctional chiral photonic and sensing platforms. In 2025, Gryko’s group synthesized a series of heterohelicenes 34a–c, featuring a 1,4-dihydropyrrolo[3,2-b]pyrrole (DHPP) core [48] (Table 10). The compounds exhibit similar absorption and emission profiles

Tautomerism and switching in 7-hydroxy-8-(azophenyl)quinoline and similar compounds

• Lidia Zaharieva,
• Vera Deneva,
• Fadhil S. Kamounah,
• Nikolay Vassilev,
• Ivan Angelov,
• Michael Pittelkow and
• Liudmil Antonov

Beilstein J. Org. Chem. 2025, 21, 1404–1421, doi:10.3762/bjoc.21.105

• positions (2–6) in 7OHQ in respect of the value for the unsubstituted 7OHQ; changes of ΔE(K-E) (b), ΔE(KE-E) (c), and ΔE(KK-K) (d), all in kcal/mol, in 1 as a function of the substitution at a different position (2–6) in the 7-hydroxyquinoline part in respect of the corresponding values for unsubstituted 1

Reactions of acryl thioamides with iminoiodinanes as a one-step synthesis of N-sulfonyl-2,3-dihydro-1,2-thiazoles

• Vladimir G. Ilkin,
• Pavel S. Silaichev,
• Valeriy O. Filimonov,
• Tetyana V. Beryozkina,
• Margarita D. Likhacheva,
• Pavel A. Slepukhin,
• Wim Dehaen and
• Vasiliy A. Bakulev

Beilstein J. Org. Chem. 2025, 21, 1397–1403, doi:10.3762/bjoc.21.104

• Chemistry for Metals and Molecules, Department of Chemistry, KU Leuven, Celestijnenlaan 200F, Leuven B-3001, Belgium 10.3762/bjoc.21.104 Abstract A one-step method has been developed for the preparation of 2,3-dihydro-2-sulfonyl-3,4,5-substituted 1,2-thiazoles by the reaction of acryl thioamides and

• used for the synthesis of a number of 2,3-dihydro-N-sulfonyl-1,2-thiazoles 3 (Scheme 2, method A). The conditions described in entry 12 (Table 1; Scheme 2, method B) are also noteworthy, since they do not require the preliminary synthesis of iodonium salts 2, which saves time and effort, however, the

• ). Using the optimal reaction conditions (method A), twenty-seven 2,3-dihydro-N-sulfonyl-1,2-thiazoles 3 were synthesized in 69–96% yields (Scheme 2, method A). According to method B (Scheme 2), five compounds 3aa–ae were obtained in moderate yields (40–70%). The formation of the final compounds starts by

N-Salicyl-amino acid derivatives with antiparasitic activity from Pseudomonas sp. UIAU-6B

• Joy E. Rajakulendran,
• Emmanuel Tope Oluwabusola,
• Michela Cerone,
• Terry K. Smith,
• Olusoji O. Adebisi,
• Adefolalu Adedotun,
• Gagan Preet,
• Sylvia Soldatou,
• Hai Deng,
• Rainer Ebel and
• Marcel Jaspars

Beilstein J. Org. Chem. 2025, 21, 1388–1396, doi:10.3762/bjoc.21.103

• new natural products, pseudomonins D–G (1–4) isolated alongside other three known compounds, pseudomonine (5), pseudomonin B (6) and salicylic acid (7), were elucidated based on high-resolution mass spectrometry, 1D and 2D NMR analyses. The absolute configurations of the threonine residue in compounds

• isolation of five phenolic siderophores with some of them exhibiting antimicrobial properties, including pseudomonins A–C and pseudomobactins A and B [15]. In this study we report the isolation and structural characterization of two previously undescribed as natural products (1 and 2) and two new compounds

• (3 and 4) isolated alongside three known compounds, pseudomonine (5), pseudomonin B (6) and salicylic acid (7) [15] from the Pseudomonas sp. UIAU-6B strain by altering the fermentation conditions using an open system shaker at room temperature [16][17][18]. Results and Discussion The bacterial strain

High-pressure activation for the solvent- and catalyst-free syntheses of heterocycles, pharmaceuticals and esters

• Kelsey Plasse,
• Valerie Wright,
• Guoshu Xie,
• R. Bernadett Vlocskó,
• Alexander Lazarev and
• Béla Török

Beilstein J. Org. Chem. 2025, 21, 1374–1387, doi:10.3762/bjoc.21.102

• reactions were carried out at 80 °C and at (a) 3.8 kbar, 1 h, (b) 2.8 kbar, 30 × 1 min cycles, (c) 2.8 kbar, 40 × 1 min cycles. The yields were determined by GC. High pressure-initiated large scale syntheses of N-aryl- and N-alkylpyrroles at about 100 g scale. Optimization of the HHP-initiated synthesis of

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

• ], oxetanocin A [22], oxetin [23], merrilactone A [24], dictyoxetane [25] and mitrephorone A [26], which were isolated by 2005, but the collection is still being expanded and more recent additions include dichrocephone B from 2013 [27], compositacin D from 2017 [28], hawaiienol A from 2018 [29] or dendroterpene

• categorised into 6 synthetic strategies as depicted in Scheme 1: a) C–O bond-forming cyclisations, b) C–C bond-forming cyclisations, c) [2 + 2] cycloadditions between carbonyls and alkenes, d) ring expansions, e) ring contractions and f) O–H insertions. In the following subchapters, these strategies will be

Recent advances in amidyl radical-mediated photocatalytic direct intermolecular hydrogen atom transfer

• Hao-Sen Wang,
• Lin Li,
• Xin Chen,
• Jian-Li Wu,
• Kai Sun,
• Xiao-Lan Chen,
• Ling-Bo Qu and
• Bing Yu

Beilstein J. Org. Chem. 2025, 21, 1306–1323, doi:10.3762/bjoc.21.100

• transfer (HAT) in photocatalytic reactions. These radicals display exceptional selectivity and efficiency in abstracting hydrogen atoms from C–H, Si–H, B–H, and Ge–H, positioning them as invaluable tools in synthetic chemistry. This review summarizes the latest advancements in the photocatalyzed generation

• and the relatively green chemistry of generating amidyl radicals. Amidyl radicals offer several advantages that enhance their applicability in organic synthesis: 1) The BDE of amidyl N–H bond is more than 105 kcal/mol, relative to the bond (C–H, Si–H, B–H, and Ge–H) which BDE is lower than 100 kcal

• amidyl radicals from HRP: (a) direct single-electron oxidation of amide HRP in the presence of photocatalyst and a base via a proton-coupled electron transfer (PCET) process by the cleavage of the N–H bond; (b) single-electron reduction of HRP catalyzed by photocatalyst via a single-electron transfer

Recent advances and future challenges in the bottom-up synthesis of azulene-embedded nanographenes

• Bartłomiej Pigulski

Beilstein J. Org. Chem. 2025, 21, 1272–1305, doi:10.3762/bjoc.21.99

• antiaromatic character of the pentagon, in contrast to pristine azulene. This results in a significantly red-shifted optical absorption at 997 nm. Therefore, compound 24 should be considered a formally antiaromatic extended indeno[1,2-b]fluorene, rather than a ‘true’ extended azulene. Similarly, Müllen and co

• with a low singlet−triplet gap. Nanographene 26, which also contains the indeno[1,2-b]fluorene structural motif, displays an extremely narrow energy gap of 0.27 eV and exhibits a pronounced open-shell biradical character, with biradical character index close to 1 (y0 = 0.92). Very recently, a similar

• products containing either two (63) or four azulene subunits (64). Analysis of NICS values revealed that the formally antiaromatic character indeno[1,2-b]fluorene units remain dominant in fused PAHs 63 and 64 resulting also in a biradical character. Considering these factors, PAHs 63 and 64 should be

Recent advances in oxidative radical difunctionalization of N-arylacrylamides enabled by carbon radical reagents

• Jiangfei Chen,
• Yi-Lin Qu,
• Ming Yuan,
• Xiang-Mei Wu,
• Heng-Pei Jiang,
• Ying Fu and
• Shengrong Guo

Beilstein J. Org. Chem. 2025, 21, 1207–1271, doi:10.3762/bjoc.21.98

• radical A. This is followed by the conversion of a substrate containing C(sp3)–H bonds adjacent to an oxygen atom into an alkyl radical intermediate B. The alkyl radical intermediate then adds to the C=C bond of N-arylacrylamide, generating a second alkyl radical intermediate C, which undergoes

• . This alkyl radical then adds across the C–C double bond in the enyne, forming an alkyl radical intermediate B, which reacts with the C–C triple bond to generate a vinyl radical intermediate C. Depending on the substitution effect at the 3-position of the acrylamide moiety, the intermediate undergoes

• -determining step. Based on these results, a detailed mechanism was proposed (Scheme 10) in which a copper-assisted homolysis of DCP generates a cumyloxyl radical A, which initiates the formation of an imidoyl radical B from the isocyanide. This radical then undergoes homolytic cleavage to yield an alkyl

Optimized synthesis of aroyl-S,N-ketene acetals by omission of solubilizing alcohol cosolvents

• Julius Krenzer and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2025, 21, 1201–1206, doi:10.3762/bjoc.21.97

• chlorides 2 and 2-methyl-N-benzylbenzothiazolium salts 3 in 1,4-dioxane as a solvent at room temp for 0.5 to 1 h produces representative aroyl-S,N-ketene acetals 1 in mostly excellent yield (Scheme 3). For comparison, the yields of the products 1 under standard (A) and new modified (B) conditions are listed

• in Table 1. The yield of compounds 1 after flash chromatography on silica gel under modified conditions (B) are significantly higher than under standard conditions (A). The results demonstrate the broad applicability of the optimized reaction conditions. Acid chlorides with electron-withdrawing (-CN

• ) and will be applied in future sequences for the generation of (hetero)aroyl-S,N-ketene acetals. Experimental Synthesis of compound 1i according to conditions B (typical procedure): 4-Fluorobenzoyl chloride (2e, 0.590 mL, 4.99 mmol, 1.00 equiv) and benzothiazolium salt 3a (1.76 g, 5.50 mmol, 1.10 equiv

Synthesis of β-ketophosphonates through aerobic copper(II)-mediated phosphorylation of enol acetates

• Alexander S. Budnikov,
• Igor B. Krylov,
• Fedor K. Monin,
• Valentina M. Merkulova,
• Alexey I. Ilovaisky,
• Liu Yan,
• Bing Yu and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2025, 21, 1192–1200, doi:10.3762/bjoc.21.96

• Alexander S. Budnikov Igor B. Krylov Fedor K. Monin Valentina M. Merkulova Alexey I. Ilovaisky Liu Yan Bing Yu Alexander O. Terent'ev N. D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation M. V. Lomonosov Moscow State

• radicals and product 3 can be described by several pathways. The direct oxidation of 2 by Cu(II) A leads to the formation of P-centered radical E and Cu(I) B. Under air atmosphere, the formed Cu(I) species B can react with molecular oxygen resulting in the formation of peroxycopper intermediate C [75][76

• hydroperoxide transfer from copper complex D with the formation of intermediate H and, therefore, regenerating Cu(I) B. Alternatively, the latter can be formed by oxidation of benzylic radical G with the formation of carbocation I. However, given that in the absence of oxygen the β-ketophosphonate was formed

Selective monoformylation of naphthalene-fused propellanes for methylene-alternating copolymers

• Kenichi Kato,
• Tatsuki Hiroi,
• Seina Okada,
• Shunsuke Ohtani and
• Tomoki Ogoshi

Beilstein J. Org. Chem. 2025, 21, 1183–1191, doi:10.3762/bjoc.21.95

• electrophilic functionalization. a) Synthesis of methylene-alternating copolymers of fully π-fused propellanes. DCE, 1,2-dichloroethane. b) 1H NMR (500 MHz, top) and 13C (126 MHz, bottom) NMR spectra of [4.3.3]_CH2OH and [4.3.3]_linear in CDCl3 at room temperature. Gas adsorption (filled circles) and desorption

• (open circles) isotherms of [3.3.3]_oligo (dark red), [3.3.3]_linear (red), [3.3.3]_branch (orange), [4.3.3]_oligo (purple), [4.3.3]_linear (blue), and [4.3.3]_branch (green). a) CO2 at 298 K and b) N2 at 77 K. Formylation of naphthalene-fused propellanes. Properties of methylene-alternating

Enhancing chemical synthesis planning: automated quantum mechanics-based regioselectivity prediction for C–H activation with directing groups

• Julius Seumer,
• Nicolai Ree and
• Jan H. Jensen

Beilstein J. Org. Chem. 2025, 21, 1171–1182, doi:10.3762/bjoc.21.94

• SMARTS pattern match than highlighted in Tomberg and colleagues [9]. The matching SMARTS pattern from Tomberg et al. [9] is shown in (a), whereas our algorithm resulted in the match shown in (b). An example highlighting the difficulties in prioritizing the SMARTS patterns. All three patterns match the

• black cross. B: Distribution of correct (green), semi-correct (yellow), and wrong (red) predictions for the same molecules, evaluated with an energy threshold of 1.0 kcal·mol−1. Molecules with five potential reaction sites that are predicted wrong by the QM workflow. The experimentally observed and

A multicomponent reaction-initiated synthesis of imidazopyridine-fused isoquinolinones

• Ashutosh Nath,
• John Mark Awad and
• Wei Zhang

Beilstein J. Org. Chem. 2025, 21, 1161–1169, doi:10.3762/bjoc.21.92

• reaction followed by the cleavage of the alkyl group to give intermediate II as a free amine. Annulation of II with CDI gave product B which is an HIV reverse transcriptase inhibitor (Scheme 1B) [17]. We have reported a three-component [3 + 2] cycloaddition followed by IMDA reaction for making heterocyclic