Synthesis, liquid crystalline behaviour and structure–property relationships of 1,3-bis(5-substituted-1,3,4-oxadiazol-2-yl)benzenes

• Afef Mabrouki,
• Malek Fouzai,
• Armand Soldera,
• Abdelkader Kriaa and
• Ahmed Hedhli

Beilstein J. Org. Chem. 2020, 16, 149–158, doi:10.3762/bjoc.16.17

• perfluoroalkyl as terminal chains were synthesized and characterized. Liquid crystal properties of the synthesized compounds have been investigated by polarizing optical microscopy, differential scanning calorimetry and X-ray diffraction techniques. Conformation effects of the synthesized products on the dipole

• compounds 2 and 4 is constituted by a rigid core (three aromatic rings) to which are attached the terminal chains. Based on this structure, some liquid crystalline mesophases were expected. Differential scanning calorimetry (DSC), polarized optical microscopy (POM) and X-ray diffraction pattern analysis

• investigated the X-ray diffraction at the mesophases in cooling and heating cycle of 2b, 4a and 4b. Figure 3 illustrates typical diffraction spectra for compound 2b. A typical X-ray pattern recorded for the SmA phase is obtained, it showed two small reflections at 23.69 Å and 15.71 Å at low angle region, and a

Synthesis of 3-alkenylindoles through regioselective C–H alkenylation of indoles by a ruthenium nanocatalyst

• Abhijit Paul,
• Debnath Chatterjee,
• Srirupa Banerjee and
• Somnath Yadav

Beilstein J. Org. Chem. 2020, 16, 140–148, doi:10.3762/bjoc.16.16

• analysis (Figure S6, Supporting Information File 1) distinctly showed the presence of Ru. The experiment also showed the presence of a small amount of oxygen, which could be attributed to the presence of some surface oxides. Powder X-ray diffraction (Figure S7, Supporting Information File 1) of the

Reversible photoswitching of the DNA-binding properties of styrylquinolizinium derivatives through photochromic [2 + 2] cycloaddition and cycloreversion

• Sarah Kölsch,
• Heiko Ihmels,
• Jochen Mattay,
• Norbert Sewald and
• Brian O. Patrick

Beilstein J. Org. Chem. 2020, 16, 111–124, doi:10.3762/bjoc.16.13

• methoxy-substituted styrylquinolizinium derivatives form the corresponding syn head-to-tail cyclobutanes in a selective [2 + 2] photocycloaddition, as revealed by X-ray diffraction analysis of the reaction products. These photodimers bind to DNA only weakly by outside-edge association, but they release

• single crystals after slow evaporation, their structure was determined by single crystal X-ray diffraction (XRD) analysis (Figure 8, cf. Supporting Information File 1). The cyclobutane 4b crystallized from water in the monoclinic space group P21/n, and the derivative 4c crystallized from water in the

Halogen-bonding-induced diverse aggregation of 4,5-diiodo-1,2,3-triazolium salts with different anions

• Xingyu Xu,
• Shiqing Huang,
• Zengyu Zhang,
• Lei Cao and
• Xiaoyu Yan

Beilstein J. Org. Chem. 2020, 16, 78–87, doi:10.3762/bjoc.16.10

• reported neutral 4-halo-1,2,3-triazolylidenes C [43], which had a carbene character with σ-donation at the carbon and a σ-hole at the halogen atom. XB is observed by single-crystal X-ray diffraction in their coinage metal complexes. Meanwhile, 4-bromo-1,2,3-triazolylidene can catalyze H/D exchange of

• via removing the iodide anion by AgOAc and CF3COOAg. A single crystal of 2-OAc suitable for X-ray diffraction analysis was obtained by slow diffusion of n-pentane into a dichloromethane solution. A single crystal of 2-TFA suitable for X-ray diffraction analysis was obtained by slow evaporation of

• mg, 31% yield. 1H NMR (400 MHz, CDCl3) δ 8.60 (d, J = 6.1 Hz, 2H), 7.57 (d, J = 6.2 Hz, 2H), 7.11 (s, 4H), 2.39 (s, 6H), 2.02 (s, 12H); 13C NMR (100 MHz, CDCl3) δ 150.0, 145.7, 143.5, 134.0, 131.6, 130.2, 121.9, 107.6, 21.4, 17.2. X-ray diffraction measurements Single crystal diffraction data for 2-I

Influence of the cis/trans configuration on the supramolecular aggregation of aryltriazoles

• Sara Tejera,
• Giada Caniglia,
• Rosa L. Dorta,
• Andrea Favero,
• Javier González-Platas and
• Jesús T. Vázquez

Beilstein J. Org. Chem. 2019, 15, 2881–2888, doi:10.3762/bjoc.15.282

• configuration through X-ray diffraction studies can be considered good approximations to the supramolecular structure of aryltriazoles in gels. Thus, these compounds showed a high degree of parallelism between the phenyltriazolyl rings, therefore revealing the presence of π–π stacking and π–bromine interactions

• /H2O, 1:2, v/v, middle right), 12 (DMSO, bottom left), and 14 (DMSO/H2O, 9:1, v/v, bottom right). ORTEP representation of the molecular structure of compound 12 (trans configuration) obtained from X-ray diffraction data. Crystal packing of compound 12 (trans configuration) in DMSO. Crystal packing of

• stabilization of the supramolecular aggregation of bis(4-bromophenyl)triazoles. The trans or cis spatial disposition of the triazole rings is highly important for gelation, with the cis configuration having higher propensity. Keywords: circular dichroism; cis/trans configuration; gels; triazole; X-ray

Facile regiodivergent synthesis of spiro pyrrole-substituted pseudothiohydantoins and thiohydantoins via reaction of [e]-fused 1H-pyrrole-2,3-diones with thiourea

• Aleksandr I. Kobelev,
• Nikita A. Tretyakov,
• Ekaterina E. Stepanova,
• Maksim V. Dmitriev,
• Michael Rubin and
• Andrey N. Maslivets

Beilstein J. Org. Chem. 2019, 15, 2864–2871, doi:10.3762/bjoc.15.280

• out that earlier, we have communicated initial data on this transformation [30][31]. However, taking into account more advanced structure elucidation methods employed in the present work (e.g., NMR, single crystal X-ray diffraction), we concluded that the structures of the products were identified

Carbazole-functionalized hyper-cross-linked polymers for CO₂ uptake based on Friedel–Crafts polymerization on 9-phenylcarbazole

• Dandan Fang,
• Xiaodong Li,
• Meishuai Zou,
• Xiaoyan Guo and
• Aijuan Zhang

Beilstein J. Org. Chem. 2019, 15, 2856–2863, doi:10.3762/bjoc.15.279

• of rough surface particles. The particles had different size and agglomerated to loose aggregates. There were plentiful pores randomly distributed among the particles. X-ray diffraction (XRD) of obtained HCPs exhibited similar diffraction patterns, only a round peak at 10°, hinting that P1–P11 were

• NETZSCH TG 209F1 TG analyzer for 40–800 °C at a heating rate of 10 °C min−1 under a nitrogen flow of 50 mL min−1. The X-ray diffraction (XRD) patterns of the as prepared polymers were collected using a PANalytical X’pert Pro MPD diffractometer with Cu Kα radiation at room temperature, with step size of

Unexpected one-pot formation of the 1H-6a,8a-epiminotricyclopenta[a,c,e][8]annulene system from cyclopentanone, ammonia and dimethyl fumarate. Synthesis of highly strained polycyclic nitroxide and EPR study

• Sergey A. Dobrynin,
• Igor A. Kirilyuk,
• Yuri V. Gatilov,
• Andrey A. Kuzhelev,
• Olesya A. Krumkacheva,
• Matvey V. Fedin,
• Michael K. Bowman and
• Elena G. Bagryanskaya

Beilstein J. Org. Chem. 2019, 15, 2664–2670, doi:10.3762/bjoc.15.259

• on silica gel 60 (70–230 mesh). X-ray diffraction data were obtained with a Bruker KAPPA APEX II diffractometer using ϕ, ω scans with Mo Kα radiation (λ = 0.71073 Å) and a graphite monochromator. CCDC 1947797 (for 1) and 1947798 (for 6) contain the supplementary crystallographic data for this paper

Nanangenines: drimane sesquiterpenoids as the dominant metabolite cohort of a novel Australian fungus, Aspergillus nanangensis

• Heather J. Lacey,
• Cameron L. M. Gilchrist,
• Andrew Crombie,
• John A. Kalaitzis,
• Daniel Vuong,
• Peter J. Rutledge,
• Peter Turner,
• John I. Pitt,
• Ernest Lacey,
• Yit-Heng Chooi and
• Andrew M. Piggott

Beilstein J. Org. Chem. 2019, 15, 2631–2643, doi:10.3762/bjoc.15.256

• identification of the nanangenines – a family of seven new and three previously reported drimane sesquiterpenoids. The structures of the nanangenines were elucidated by detailed spectroscopic analysis supported by single crystal X-ray diffraction studies. The compounds were assayed for in vitro activity against

• 7), and three acylated drimanes, nanangenines F–H (8–10), which are putative biosynthetic intermediates. The structures of 1–10 were elucidated by detailed spectroscopic analysis, while absolute configurations were determined by single crystal X-ray diffraction analysis of selected analogues. High

• strobilactone B, previously reported from A. ustus [29], with the only difference being hydroxylation at C-1 in 1, instead of at C-2. Therefore, the structure of 1 was assigned as shown in Figure 1. The absolute configuration of 1 was confirmed to be 1R,5S,6R,9R,13R by single crystal X-ray diffraction analysis

1,5-Phosphonium betaines from N-triflylpropiolamides, triphenylphosphane, and active methylene compounds

• Vito A. Fiore,
• Chiara Freisler and
• Gerhard Maas

Beilstein J. Org. Chem. 2019, 15, 2603–2611, doi:10.3762/bjoc.15.253

• fractionating crystallization. Structure determination by X-ray diffraction analysis revealed marked conformational differences around the CH–C(O–) single bond of E and Z-isomers and extended charge delocalization in the anionic part. Keywords: betaines; multi-component reactions; N-triflylamides; phospha

• vinylogues of recently reported acylphosphonium zwitterions [25]. Structural studies The solid-state molecular structures of betaines E-3a, E-3b, E-3e and Z-3e were determined by single-crystal X-ray diffraction analysis and are shown in Figures 2–5. Some data characterizing the bonding geometry of the P+–C1

Formation of alkyne-bridged ferrocenophanes using ring-closing alkyne metathesis on 1,1’-diacetylenic ferrocenes

• Celine Bittner,
• Dirk Bockfeld and
• Matthias Tamm

Beilstein J. Org. Chem. 2019, 15, 2534–2543, doi:10.3762/bjoc.15.246

• solutions of 1a and 1b after layering with pentane or hexane, respectively, crystals suitable for X-ray diffraction analysis could be obtained. The corresponding ORTEP drawings are given in Figure 3 and Figure 4. Ferrocene 1a crystallises in the orthorhombic space group Pca21, while the analogues compound

• disorder on the iron position. Unfortunately, no single crystals for X-ray diffraction analysis could be obtained with such disorder being absent. For the catalytic RCAM (Scheme 1), the substrates 1a and 1b were dissolved in toluene at high dilution (4.5 mM), and the catalyst MoF6 (2 mol %) was added as a

• experimental section in Supporting Information File 1). Crystals of 2a suitable for X-ray diffraction analysis could be obtained from a hot saturated solution in toluene after cooling to −28 °C. An ORTEP drawing is given in Figure 5. The ferrocenophane 2a crystallises in the orthorhombic space group Pbcn with

Self-assembled coordination thioether silver(I) macrocyclic complexes for homogeneous catalysis

• Zhen Cao,
• Aline Lacoudre,
• Cybille Rossy and
• Brigitte Bibal

Beilstein J. Org. Chem. 2019, 15, 2465–2472, doi:10.3762/bjoc.15.239

• -atropisomer, as revealed by X-ray diffraction. This alkylaryl thioether ligand (L) formed different macrocyclic complexes by coordination with silver(I) salts depending on the nature of the anion: M2L2 for AgOTf and AgOTFA, M6L4 for AgNO3. A discrete M2L complex was obtained in the presence of bulky PPh3AgOTf

• for 1a, AgOTFA for 1b, AgNO3 for 1c and PPh3AgOTf for 1d. Crystallographic structures of silver complexes Single crystals of 1a, 1c and 1d suitable for X-ray diffraction analysis were grown from the slow diffusion of hexane into a solution of each complex in dichloromethane. Interestingly, each

• )–1 ligands). The X-ray diffraction of monocrystals 1a revealed the formation of (R,S–1)2·(AgOTf)2 macrocycles driven by silver(I) coordination (Figure 1). The two ligands are facing through the coordination of one syn-thioether group to the same silver cation. Two different crystals were isolated and

Reversible switching of arylazopyrazole within a metal–organic cage

• Anton I. Hanopolskyi,
• Soumen De,
• Michał J. Białek,
• Yael Diskin-Posner,
• Liat Avram,
• Moran Feller and
• Rafal Klajn

Beilstein J. Org. Chem. 2019, 15, 2398–2407, doi:10.3762/bjoc.15.232

• protons are correlated with H1, H3, and H7, whereas the Hc protons are correlated with H4, H8, and H5 (see the partial NOE spectrum in Figure 2; see below for further analysis of this spectrum). Single crystals of (E-1)22 suitable for X-ray diffraction were obtained by slow water evaporation from an

• guest molecules inside the cage was demonstrated independently by NMR spectroscopy and single-crystal X-ray diffraction. Exposure to UV light resulted in an E→Z isomerization of the guest, which was accompanied by the expulsion of one of two guest molecules from the cage. Different from the previously

• -ray diffraction. To obtain hints about the packing of Z-1 within 2, we therefore performed density functional theory (DFT) calculations. Compared with the complex before photoisomerization, the cage in (Z-1)2 is severely distorted (Figure 5; see also Supporting Information File 3), assuming a bowl

Regioselective Pd-catalyzed direct C1- and C2-arylations of lilolidine for the access to 5,6-dihydropyrrolo[3,2,1-ij]quinoline derivatives

• Hai-Yun Huang,
• Haoran Li,
• Thierry Roisnel,
• Jean-François Soulé and
• Henri Doucet

Beilstein J. Org. Chem. 2019, 15, 2069–2075, doi:10.3762/bjoc.15.204

• lilolidines were detected in very low yields by GC–MS analysis of the crude mixtures. The structure of 20 was confirmed by X-ray diffraction. As α-arylated lilolidines can be easily obtained under the reaction conditions shown in Scheme 2, the synthesis of α,β-diarylated 5,6-dihydropyrrolo[3,2,1-ij]quinolines

• ) catalyst associated to KOAc provided the desired diarylated lilolidines 23–26 in 55–87% yields. The structure of 23 was confirmed by X-ray diffraction. Finally, the synthesis of 5,6-dihydrodibenzo[a,c]pyrido[3,2,1-jk]carbazoles via β-arylation of the previously obtained α-arylated lilolidines followed by

1,2,3,4-Tetrahydro-1,4,5,8-tetraazaanthracene revisited: properties and structural evidence of aromaticity loss

• Arnault Heynderickx,
• Sébastien Nénon,
• Olivier Siri,
• Vladimir Lokshin and
• Vladimir Khodorkovsky

Beilstein J. Org. Chem. 2019, 15, 2059–2068, doi:10.3762/bjoc.15.203

• expected for the bis-acylated products. Molecular structures The molecular structures of compounds 3, 6a, and 7a have been established by an X-ray diffraction study. The molecular geometry is strongly affected by the presence of networks of intramolecular short distances: =N···H–N< (derivatives 3 and 7a

Synthesis of benzo[d]imidazo[2,1-b]benzoselenoazoles: Cs₂CO₃-mediated cyclization of 1-(2-bromoaryl)benzimidazoles with selenium

• Mio Matsumura,
• Yuki Kitamura,
• Arisa Yamauchi,
• Yoshitaka Kanazawa,
• Yuki Murata,
• Tadashi Hyodo,
• Kentaro Yamaguchi and
• Shuji Yasuike

Beilstein J. Org. Chem. 2019, 15, 2029–2035, doi:10.3762/bjoc.15.199

• was fully characterized by 1H and 13C NMR spectroscopy and HRMS, and further confirmed by single-crystal X-ray diffraction (XRD) analysis. The ORTEP drawing and packing structure of 2a obtained from the single crystal XRD analysis are illustrated in Figure 1. The crystal structure contained two

Synthesis and anion binding properties of phthalimide-containing corona[6]arenes

• Meng-Di Gu,
• Yao Lu and
• Mei-Xiang Wang

Beilstein J. Org. Chem. 2019, 15, 1976–1983, doi:10.3762/bjoc.15.193

• -corona[6]arenes in the solid state, high quality single crystals of 3a were grown at room temperature from diffusion of diethyl ether vapor into the solution of 3a in acetonitrile. X-ray diffraction analysis revealed that the macrocycle 3a adopted an interesting conformation. As depicted in Figure 1, it

Synthesis, enantioseparation and photophysical properties of planar-chiral pillar[5]arene derivatives bearing fluorophore fragments

• Guojuan Li,
• Chunying Fan,
• Guo Cheng,
• Wanhua Wu and
• Cheng Yang

Beilstein J. Org. Chem. 2019, 15, 1601–1611, doi:10.3762/bjoc.15.164

• Sp configured isomer, based on calculations as well as single-crystal X-ray diffraction published recently [20]. Thus, the absolute configuration of the first fraction was assigned to be Sp and the second fraction was assigned to the Rp isomer. Unexpectedly, no induced CD signals of DPA units at 360

Synthesis of ([1,2,4]triazolo[4,3-a]pyridin-3-ylmethyl)phosphonates and their benzo derivatives via 5-exo-dig cyclization

• Aleksandr S. Krylov,
• Artem A. Petrosian,
• Julia L. Piterskaya,
• Nataly I. Svintsitskaya and
• Albina V. Dogadina

Beilstein J. Org. Chem. 2019, 15, 1563–1568, doi:10.3762/bjoc.15.159

• spectroscopy, high-resolution mass spectrometry, as well as single crystal X-ray diffraction. Next, under the conditions applied for the preparation of compounds 3–8, the reaction of chloroethynylphosphonates with 2-hydrazinylquinoline (1g) and 1-hydrazinylisoquinoline (1h) resulted in the formation of [1,2,4

• of spin–spin interaction with the phosphorus nucleus at 23.43–28.99 ppm (1JСР = 143 Hz) and 53.5–72.1 ppm (2JCP = 7 Hz), respectively. In addition, the structure of phosphonate 14b was unambiguously proved by single crystal X-ray diffraction analysis. Probably, the reaction proceeds through the

• Institute of Technology, the Center for Chemical Analysis and Materials, and the Center for X-ray Diffraction Methods of Saint-Petersburg State University.

Different reactivity of phosphorylallenes under the action of Brønsted or Lewis acids: a crucial role of involvement of the P=O group in intra- or intermolecular interactions at the formation of cationic intermediates

• Stanislav V. Lozovskiy,
• Alexander Yu. Ivanov and
• Aleksander V. Vasilyev

Beilstein J. Org. Chem. 2019, 15, 1491–1504, doi:10.3762/bjoc.15.151

• no. 18-13-00008). Spectral studies were performed at the Center for Magnetic Resonance, Center for Chemical Analysis and Materials Research, and Research Center for X-ray Diffraction Studies of Saint Petersburg State University, Saint Petersburg, Russia.

Introduction of an isoxazoline unit to the β-position of porphyrin via regioselective 1,3-dipolar cycloaddition reaction

• Xiujun Liu,
• Xiang Ma and
• Yaqing Feng

Beilstein J. Org. Chem. 2019, 15, 1434–1440, doi:10.3762/bjoc.15.143

• linked to the porphyrin is still elusive. Later, a single crystal of 3a was obtained by diffusion of n-hexane to the solution of 3a in CHCl3 at 23 °C. The structure of 3a was unambiguously established by single-crystal X-ray diffraction analysis. Compound 3a crystallized in the monoclinic with space

Borylation and rearrangement of alkynyloxiranes: a stereospecific route to substituted α-enynes

• Ruben Pomar Fuentespina,
• José Angel Garcia de la Cruz,
• Gabriel Durin,
• Victor Mamane,
• Jean-Marc Weibel and
• Patrick Pale

Beilstein J. Org. Chem. 2019, 15, 1416–1424, doi:10.3762/bjoc.15.141

• lithium observed by X-ray diffraction in the lithiated o-trifluoromethylstyrene oxide [37] may be further elongated due to hindrance introduced by the trans-substituent adjacent to the lithium atom of the second oxirane in the dimer (Scheme 2, entry 5). Such effect may facilitate the formation of the

Selenophene-containing heterotriacenes by a C–Se coupling/cyclization reaction

• Pierre-Olivier Schwartz,
• Sebastian Förtsch,
• Astrid Vogt,
• Elena Mena-Osteritz and
• Peter Bäuerle

Beilstein J. Org. Chem. 2019, 15, 1379–1393, doi:10.3762/bjoc.15.138

• starting material, but also ring fusion to selenophene was achieved by Cu-catalyzed C–Se cross-coupling reaction [28]. The detailed geometric structure and the packing behaviour in the solid state of triacenes 2–4 have been elucidated by single crystal X-ray structure analysis and X-ray diffraction on

Formation of an unexpected 3,3-diphenyl-3H-indazole through a facile intramolecular [2 + 3] cycloaddition of the diazo intermediate

• Andrew T. King,
• Hugh G. Hiscocks,
• Lidia Matesic,
• Mohan Bhadbhade,
• Roger Bishop and
• Alison T. Ung

Beilstein J. Org. Chem. 2019, 15, 1347–1354, doi:10.3762/bjoc.15.134

• with dimensions of 0.11 × 0.19 × 0.22 mm, selected under the polarising microscope (Leica M165Z), was mounted on a MicroMount (MiTeGen, USA) consisting of a thin polymer tip with a wicking aperture. The X-ray diffraction measurements were carried out on a Bruker kappa-II CCD diffractometer at 150 K

Synthesis of non-racemic 4-nitro-2-sulfonylbutan-1-ones via Ni(II)-catalyzed asymmetric Michael reaction of β-ketosulfones

• Alexander N. Reznikov,
• Anastasiya E. Sibiryakova,
• Marat R. Baimuratov,
• Eugene V. Golovin,
• Victor B. Rybakov and
• Yuri N. Klimochkin

Beilstein J. Org. Chem. 2019, 15, 1289–1297, doi:10.3762/bjoc.15.127

• Information Supporting Information File 220: Experimental procedures, copies of NMR, FTIR, mass spectra, HPLC and X-ray diffraction data. Acknowledgements This work was supported by the Russian Science Foundation (Grant No. 18-13-00447) and a STOE STADI VARI PILATUS-100K diffractometer purchased by MSU