The charge transport properties of dicyanomethylene-functionalised violanthrone derivatives

• Sondos A. J. Almahmoud,
• Joseph Cameron,
• Dylan Wilkinson,
• Michele Cariello,
• Claire Wilson,
• Alan A. Wiles,
• Peter J. Skabara and
• Graeme Cooke

Beilstein J. Org. Chem. 2024, 20, 2921–2930, doi:10.3762/bjoc.20.244

• single-crystal X-ray analysis were obtained by slow evaporation of a dichloromethane/isopropanol solution of 3b. The crystal structure of 3b, displayed in Figure 4, shows a very similar twisted conformation of the core of the molecule to that of the related methoxy-substituted structure obtained from

Synthesis of pyrrole-fused dibenzoxazepine/dibenzothiazepine/triazolobenzodiazepine derivatives via isocyanide-based multicomponent reactions

• Marzieh Norouzi,
• Mohammad Taghi Nazeri,
• Ahmad Shaabani and
• Behrouz Notash

Beilstein J. Org. Chem. 2024, 20, 2870–2882, doi:10.3762/bjoc.20.241

• analysis, mass spectrum, and IR are consistent with the structure (for details see Supporting Information File 1). Finally, a single crystal X-ray analysis of compound 6a was performed, confirming the structure (Figure 4). The proposed mechanism for an isocyanide-based multicomponent domino reaction for

Copper-catalyzed yne-allylic substitutions: concept and recent developments

• Shuang Yang and
• Xinqiang Fang

Beilstein J. Org. Chem. 2024, 20, 2739–2775, doi:10.3762/bjoc.20.232

• radical-involved mechanism. In addition, a positive nonlinear relationship between the product and ligand indicated that the dinuclear copper is the active catalyst, which was also proved by single crystal X-ray analysis. However, kinetic experiments showed the reaction is first-order on copper, implying

Anion-dependent ion-pairing assemblies of triazatriangulenium cation that interferes with stacking structures

• Yohei Haketa,
• Takuma Matsuda and
• Hiromitsu Maeda

Beilstein J. Org. Chem. 2024, 20, 2567–2576, doi:10.3762/bjoc.20.215

• synthesized to investigate the interactions for the bulky cation. Single-crystal X-ray analysis of the TATA+ ion pairs revealed solid-state ion-pairing assemblies without stacking at the cationic π-planes. The TATA+ cation showed counteranion-dependent assembly structures, with smaller counteranions located

• at the top of TATA+ and bulkier counteranions displaced from the TATA+ plane to interact with the surrounding TATA+. Keywords: charged π-electronic systems; ion pairs; single-crystal X-ray analysis; solid-state assemblies; triazatriangulenium cation; Introduction Triangulenium cations [1][2] have

• characterized by single-crystal X-ray diffraction analysis. Method for single-crystal X-ray analysis Crystallographic data are summarized in Table 1. A single crystal of 2+-Cl− was obtained by vapor diffusion of n-heptane into a CHCl3 solution. The data crystal was a red prism of approximate dimensions 0.20 mm

Synthesis, electrochemical properties, and antioxidant activity of sterically hindered catechols with 1,3,4-oxadiazole, 1,2,4-triazole, thiazole or pyridine fragments

• Daria A. Burmistrova,
• Andrey Galustyan,
• Nadezhda P. Pomortseva,
• Kristina D. Pashaeva,
• Maxim V. Arsenyev,
• Oleg P. Demidov,
• Mikhail A. Kiskin,
• Andrey I. Poddel’sky,
• Nadezhda T. Berberova and
• Ivan V. Smolyaninov

Beilstein J. Org. Chem. 2024, 20, 2378–2391, doi:10.3762/bjoc.20.202

• corresponding thiones. The yield of reaction products ranges from 42 to 80%. The crystal structures of catechols with 3-nitropyridine or 1,3,4-oxadiazole-2(3H)-thione moieties were established by single-crystal X-ray analysis. The possibility of forming intra- and intermolecular hydrogen bonds has been

• ), HRMS, and elemental analysis. The molecular structures of compounds 5, 6 and 8 in crystal state were determined by single-crystal X-ray analysis. X-ray data The X-ray suitable crystals 5, 6·0.5CH3CN, and 8 were grown by slow recrystallization of the compounds from acetonitrile solutions. The unit cells

Heterocycle-guided synthesis of m-hetarylanilines via three-component benzannulation

• Andrey R. Galeev,
• Maksim V. Dmitriev,
• Alexander S. Novikov and
• Andrey N. Maslivets

Beilstein J. Org. Chem. 2024, 20, 2208–2216, doi:10.3762/bjoc.20.188

• reaction was expected, Figure 2) with morpholine under previously found conditions (Scheme 2). To our delight, the meta-1,2,4-oxadiazole aniline 3ab, formed by the sequence of aldol-type reactions, was isolated in 80% yield and its structure was confirmed by NMR and single crystal X-ray analysis (CCDC

Diastereoselective synthesis of highly substituted cyclohexanones and tetrahydrochromene-4-ones via conjugate addition of curcumins to arylidenemalonates

• Deepa Nair,
• Abhishek Tiwari,
• Banamali Laha and
• Irishi N. N. Namboothiri

Beilstein J. Org. Chem. 2024, 20, 2016–2023, doi:10.3762/bjoc.20.177

• undergoing yet another diastereoselective 6-endo-trig intramolecular oxa-Michael addition. The structure and stereochemistry of compounds 3 and 4 were confirmed by 1H-1H-COSY and 1H-1H-NOESY NMR experiments. This was further unambiguously established by single crystal X-ray analysis of a representative

Radical reactivity of antiaromatic Ni(II) norcorroles with azo radical initiators

• Siham Asyiqin Shafie,
• Ryo Nozawa,
• Hideaki Takano and
• Hiroshi Shinokubo

Beilstein J. Org. Chem. 2024, 20, 1967–1972, doi:10.3762/bjoc.20.172

• toluene (Scheme 1). The reaction smoothly proceeded to afford dialkylated macrocycle 2a in 92% yield. In addition to 2a, monoalkylated product 3a and dipyrrin dimer 4a were obtained as minor products in 4% and 3% yield, respectively. The structure of 2a was unambiguously confirmed by single-crystal X-ray

• analysis, which revealed that two alkyl substituents were located on the same side of the molecule (Figure 2a). Compared to the planar structure of 1 (Figure 2b) [2], 2a displays a nonplanar structure due to the sp3 carbon atoms adjacent to the nitrogen atoms. The 1H NMR spectrum of 2a confirmed that the

Synthesis of indano[60]fullerene thioketone and its application in organic solar cells

• Yong-Chang Zhai,
• Shimon Oiwa,
• Shinobu Aoyagi,
• Shohei Ohno,
• Tsubasa Mikie,
• Jun-Zhuo Wang,
• Hirofumi Amada,
• Koki Yamanaka,
• Kazuhira Miwa,
• Naoyuki Imai,
• Takeshi Igarashi,
• Itaru Osaka and
• Yutaka Matsuo

Beilstein J. Org. Chem. 2024, 20, 1270–1277, doi:10.3762/bjoc.20.109

• -withdrawing substituents. Computational studies with density functional theory revealed the unique vibrations of the thioketone group in FIDS. The molecular structure of FIDS was confirmed by single-crystal X-ray analysis. Bulk heterojunction organic solar cells using three evaporable fullerene derivatives

Competing electrophilic substitution and oxidative polymerization of arylamines with selenium dioxide

• Vishnu Selladurai and
• Selvakumar Karuthapandi

Beilstein J. Org. Chem. 2024, 20, 1221–1235, doi:10.3762/bjoc.20.105

• methyl anthranilate with SeO2 (vide infra), which was also supported by single-crystal X-ray analysis. However, for aniline, in addition to the major polymerization and poor selenation process, solvent oxidation was also noted. Importantly, through column chromatography, the oxamide derivative 3 formed

• account. Characterization of the organoselenium compounds by HRMS, 1H, and 13C NMR was supported by 77Se NMR and single-crystal X-ray analysis in order to confirm the identity of the compounds. Experimental General procedures All syntheses were carried out using the standard Schlenk line in a nitrogen

Structure–property relationships in dicyanopyrazinoquinoxalines and their hydrogen-bonding-capable dihydropyrazinoquinoxalinedione derivatives

• Tural N. Akhmedov,
• Ajeet Kumar,
• Daken J. Starkenburg,
• Kyle J. Chesney,
• Khalil A. Abboud,
• Novruz G. Akhmedov,
• Jiangeng Xue and
• Ronald K. Castellano

Beilstein J. Org. Chem. 2024, 20, 1037–1052, doi:10.3762/bjoc.20.92

• converting the DCPQs into hydrogen-bonding capable DPQDs. These include modulation of frontier MO energies, higher molar extinction coefficients, and on-average higher thermal stability (where in some cases the 5% weight loss temperature increased by up to 100 °C). Single-crystal X-ray analysis of DPQD

• -crystal X-ray analysis of 2b, and its important structural parameters were compared with that of 2a (#CCDC 227464) reported in the literature [25]. An improved 2D nanostructure through highly ordered organization facilitated by H-bonding is revealed. Notably, the C–C distance between two carbonyl groups

• X-ray analysis of other DPQDs 5b and 6b did not reveal a herringbone lattice pattern, as shown in Tables S5 and S6 and Figures S42–S45 (Supporting Information File 1). In the case of 5b, this is presumably due to the twisted phenyl rings that dictate the packing arrangement. Nonetheless, close π

Enhanced host–guest interaction between [10]cycloparaphenylene ([10]CPP) and [5]CPP by cationic charges

• Eiichi Kayahara,
• Yoshiyuki Mizuhata and
• Shigeru Yamago

Beilstein J. Org. Chem. 2024, 20, 436–444, doi:10.3762/bjoc.20.38

• observations also agree well with the change in oxidation and reduction potentials upon complex formation observed in the electrochemical analysis. The double-layered structure of the complex was unambiguously determined by single-crystal X-ray analysis (Figure 7), which was performed on a crystal obtained by

Photochromic derivatives of indigo: historical overview of development, challenges and applications

• Gökhan Kaplan,
• Zeynel Seferoğlu and
• Daria V. Berdnikova

Beilstein J. Org. Chem. 2024, 20, 228–242, doi:10.3762/bjoc.20.23

• of indigo in 1) DMSO, 2) DMF, 3) N-methyl-2-pyrrolidone. Bond length in the indigo molecule obtained from the single crystal X-ray analysis [12], the typical bond lengths in organic compounds [15] and the main resonance structures of indigo. The structure of the indigo chromophore (H-chromophore

Comparison of glycosyl donors: a supramer approach

• Anna V. Orlova,
• Nelly N. Malysheva,
• Maria V. Panova,
• Nikita M. Podvalnyy,
• Michael G. Medvedev and
• Leonid O. Kononov

Beilstein J. Org. Chem. 2024, 20, 181–192, doi:10.3762/bjoc.20.18

• NMR (282 MHz, acetone-d6, δ, ppm) −77.1; HRESIMS (m/z): [M + Na]+ calcd for C22H24Cl2F3NNaO10S, 644.0342; found, 644.0349 . For the details of the single crystal X-ray analysis data for compound 7 (CCDC 1843708) see Supporting Information File 1 and Supporting Information File 2. Typical glycosylation

• sialylation reaction. TFA = CF3CO; ClAc = ClCH2CO. Synthesis of sialyl donor 2. SR values and types of supramers in solutions of sialyl donors 1 and 2 at different concentrations. Supporting Information Supporting Information File 3: Copies of NMR spectra for all new compounds, single crystal X-ray analysis

Using the phospha-Michael reaction for making phosphonium phenolate zwitterions

• Matthias R. Steiner,
• Max Schmallegger,
• Larissa Donner,
• Johann A. Hlina,
• Christoph Marschner,
• Judith Baumgartner and
• Christian Slugovc

Beilstein J. Org. Chem. 2024, 20, 41–51, doi:10.3762/bjoc.20.6

• modular synthesis of stable phosphonium phenolate zwitterions bearing additional functional groups. The bonding situation in the zwitterions was studied by NMR and UV–vis spectroscopies and single-crystal X-ray analysis of selected representatives. The zwitterions exhibit negative solvatochromism and

Photoredox catalysis harvesting multiple photon or electrochemical energies

• Mattia Lepori,
• Simon Schmid and
• Joshua P. Barham

Beilstein J. Org. Chem. 2023, 19, 1055–1145, doi:10.3762/bjoc.19.81

Bromination of endo-7-norbornene derivatives revisited: failure of a computational NMR method in elucidating the configuration of an organic structure

• Demet Demirci Gültekin,
• Arif Daştan,
• Yavuz Taşkesenligil,
• Cavit Kazaz,
• Yunus Zorlu and
• Metin Balci

Beilstein J. Org. Chem. 2023, 19, 764–770, doi:10.3762/bjoc.19.56

• irrefutably by X-ray crystallography, which would provide the ultimate structural confirmation. Toward that end, we resynthesized the molecule 6, isolated a sample and subjected it to single crystal X-ray analysis, which provided the ultimate final piece of evidence (Figure 8). Additional crystallographic

An accelerated Rauhut–Currier dimerization enabled the synthesis of (±)-incarvilleatone and anticancer studies

• Tharun K. Kotammagari,
• Sweta Misra,
• Sayantan Paul,
• Sunita Kunte,
• Rajesh G. Gonnade,
• Manas K. Santra and
• Asish K. Bhattacharya

Beilstein J. Org. Chem. 2023, 19, 204–211, doi:10.3762/bjoc.19.19

• configuration of each enantiomer was determined by single-crystal X-ray analysis. In addition, a one-pot synthesis of (±)-incarviditone has been achieved from rac-rengyolone by using KHMDS as a base. We have also assessed the anticancer activity of all the synthesized compounds in breast cancer cells

• structure of rac-incarvilleatone (1) was determined by spectroscopic methods and single crystal X-ray analysis. However, they were unable to obtain single crystals of either of the enantiomers (−)-incarvilleatone [(−)-1] and (+)-incarvilleatone [(+)-1]. (±)-Incarviditone (2), a novel benzofuranone dimer was

• 331.1150 corresponding to the C16H20O6Na [M + Na]+ ion. After some efforts, to our delight, we could obtain single crystals of (±)-4 using EtOAc as a solvent. Finally, the formation of heterodimerized dihydroxy RC product (±)-4 was confirmed by single-crystal X-ray analysis [16]. It is pertinent to mention

Catalytic aza-Nazarov cyclization reactions to access α-methylene-γ-lactam heterocycles

• Bilge Banu Yagci,
• Selin Ezgi Donmez,
• Onur Şahin and
• Yunus Emre Türkmen

Beilstein J. Org. Chem. 2023, 19, 66–77, doi:10.3762/bjoc.19.6

• -Nazarov cyclization of the allyl-substituted imine substrate afforded α-methylene-γ-lactam product 19m in 56% yield. In our previous study, the relative stereochemistry of a tricyclic aza-Nazarov product obtained from a 3,4-dihydroisoquinoline derivative was secured by single-crystal X-ray analysis [35

• -lactam heterocycles 19 in up to 76% yield and with good to high diastereoselectivities (4.3:1 to 16:1). We have demonstrated the scalability of the reaction with a gram-scale example. The relative stereochemistry of the α-methylene-γ-lactam products 19 has been determined via the single-crystal X-ray

• X-ray analysis revealed that the relative stereochemistry of lactam 19l with the isobutyl and phenyl groups in a trans arrangement (Figure 1, CCDC 2116978). This finding confirms that both cyclic and acyclic imines undergo the aza-Nazarov cyclization developed in this work via the same

Inclusion complexes of the steroid hormones 17β-estradiol and progesterone with β- and γ-cyclodextrin hosts: syntheses, X-ray structures, thermal analyses and API solubility enhancements

• Alexios I. Vicatos,
• Zakiena Hoossen and
• Mino R. Caira

Beilstein J. Org. Chem. 2022, 18, 1749–1762, doi:10.3762/bjoc.18.184

• are isostructural, all of the salient structural features illustrated above and below for the γ-CD·PRO crystal are common to the γ-CD·BES crystal, which was not amenable to single crystal X-ray analysis. Solubility analysis Solubility determinations for the four native CD inclusion complexes (β-CD·BES

A novel bis-triazole scaffold accessed via two tandem [3 + 2] cycloaddition events including an uncatalyzed, room temperature azide–alkyne click reaction

• Ksenia Malkova,
• Andrey Bubyrev,
• Vasilisa Krivovicheva,
• Dmitry Dar’in,
• Alexander Bunev and
• Mikhail Krasavin

Beilstein J. Org. Chem. 2022, 18, 1636–1641, doi:10.3762/bjoc.18.175

• reaction conditions were not further optimized (Scheme 1). The structure of tetracyclic product 5a was unequivocally confirmed by 1H and 13C NMR as well as single-crystal X-ray analysis. Compound 5a is representative of the hitherto undescribed bistriazole benzodiazepine scaffold. However, 5,6,7,8

• intermediate before the click reaction was established by 1H NMR analysis of the reaction mixture). However, the product of this two-step, one-pot reaction (19) was isolated in respectable 61% yield. The structure of compound 19 was confirmed by the single-crystal X-ray analysis which demonstrated that the

• although the yield of product 21 was diminished compared to that of unsubstituted compound 5a. The structure of compound 21 was also confirmed by the single-crystal X-ray analysis (Scheme 3). All compounds were tested against lung cancer cell lines A549 and NCI-H460 and did not show any appreciable effect

A facile approach to spiro[dihydrofuran-2,3'-oxindoles] via formal [4 + 1] annulation reaction of fused 1H-pyrrole-2,3-diones with diazooxindoles

• Pavel A. Topanov,
• Anna A. Maslivets,
• Maksim V. Dmitriev,
• Irina V. Mashevskaya,
• Yurii V. Shklyaev and
• Andrey N. Maslivets

Beilstein J. Org. Chem. 2022, 18, 1532–1538, doi:10.3762/bjoc.18.162

• close to that of the products obtained from FPDs annulated with a benzoxazine fragment. The structures of products 3aa, 3ab, and 3ha were approved by single crystal X-ray analysis (CCDC 2201614, CCDC 2201616, CCDC 2201615). We also decided to study the effect the benzo-annulated moiety in FPDs has on

• crystal X-ray analysis (CCDC 2201614). As evinced by the NMR data, only one diastereomer of product 3aa was obtained. Contrary to the isoxazole-annulated products of a [3 + 2] cycloaddition of nitrones to FPDs [35], product 3aa appears to be stable on storage in solution, which was confirmed by the fact

• the solution being turned from purple to red. The starting FPD 1a is bright violet; thus, the disappearance of the violet color was used as an indicator of the reaction’s completion. Product 3aa was isolated as yellow crystals in 73% yield and characterized by NMR, IR, and mass spectra, and single

Facile and diastereoselective arylation of the privileged 1,4-dihydroisoquinolin-3(2H)-one scaffold

• Dmitry Dar’in,
• Grigory Kantin,
• Alexander Bunev and
• Mikhail Krasavin

Beilstein J. Org. Chem. 2022, 18, 1070–1078, doi:10.3762/bjoc.18.109

• of compound 9a, by single-crystal X-ray analysis. A curious and somewhat unexpected result was obtained when trying to employ N-formyl-N-methylaniline as an arene in the TfOH-promoted arylation of 10a. Instead of the anticipated product 9aa, 73% yield of predominantly trans-configured formate ester

• 16 was obtained and its structure was confirmed by single-crystal X-ray analysis. Presumably, the formation of ester 16 can be justified by the trapping of the carbocation intermediate 17 (vide infra) by the formamide carbonyl oxygen atom followed by hydrolysis of the iminium moiety (Scheme 4

• characterized). cCompound 14 was identified as the reaction product. Preparation of 4-diazo-3(2H)-isoquinolones 10. aConfirmed by single-crystal X-ray crystallography (see Supporting Information File 1). TfOH-promoted arylation of diazo substrates 10. aStructure confirmed by single-crystal X-ray analysis

Synthesis of novel alkynyl imidazopyridinyl selenides: copper-catalyzed tandem selenation of selenium with 2-arylimidazo[1,2-a]pyridines and terminal alkynes

• Mio Matsumura,
• Kaho Tsukada,
• Kiwa Sugimoto,
• Yuki Murata and
• Shuji Yasuike

Beilstein J. Org. Chem. 2022, 18, 863–871, doi:10.3762/bjoc.18.87

• single product, and the regiochemistry of 5-selanyltriazole 8 was confirmed by single crystal X-ray analysis (see Supporting Information File 3). The reaction performed using 10 mol % of CuI and PMDETA as catalytic system afforded only a small amount of product 8 (12%). Based on the results obtained in

Mechanochemical halogenation of unsymmetrically substituted azobenzenes

• Dajana Barišić,
• Mario Pajić,
• Ivan Halasz,
• Darko Babić and
• Manda Ćurić

Beilstein J. Org. Chem. 2022, 18, 680–687, doi:10.3762/bjoc.18.69

• % yields, respectively, as confirmed by NMR spectroscopy (Figures S82–S91 in Supporting Information File 1). Additional support for the formation of succinimide products was provided by the molecular structure of L4-III, resolved by single-crystal X-ray analysis (Figure 3 and Figure S33 and Table S1 in