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

Doebner-type pyrazolopyridine carboxylic acids in an Ugi four-component reaction

• Maryna V. Murlykina,
• Oleksandr V. Kolomiets,
• Maryna M. Kornet,
• Yana I. Sakhno,
• Sergey M. Desenko,
• Victoriya V. Dyakonenko,
• Svetlana V. Shishkina,
• Oleksandr A. Brazhko,
• Vladimir I. Musatov,
• Alexander V. Tsygankov,
• Erik V. Van der Eycken and
• Valentyn A. Chebanov

Beilstein J. Org. Chem. 2019, 15, 1281–1288, doi:10.3762/bjoc.15.126

• -(4-chlorophenyl)-2-oxoethyl)-6-(4-methoxyphenyl)-3-methyl-N-p-tolyl-1H-pyrazolo[3,4-b]pyridine-4-carboxamide (11n) according to X-ray diffraction data. Non-hydrogen atoms are presented as thermal ellipsoids with 50% probability. An overview of heterocyclic acids used in the Ugi reaction. Synthesis of

Bambusuril analogs based on alternating glycoluril and xylylene units

• Tomáš Lízal and
• Vladimír Šindelář

Beilstein J. Org. Chem. 2019, 15, 1268–1274, doi:10.3762/bjoc.15.124

• gratefully acknowledged for the financial support of the measurements at the CF X-ray diffraction and Bio-SAXS and CF Proteomic.

N-doped carbon dots covalently functionalized with pillar[5]arenes for Fe³⁺ sensing

• Jia Gao,
• Ming-Xue Wu,
• Dihua Dai,
• Zhi Cai,
• Yue Wang,
• Wenhui Fang,
• Yan Wang and
• Ying-Wei Yang

Beilstein J. Org. Chem. 2019, 15, 1262–1267, doi:10.3762/bjoc.15.123

• stretching vibration of C–N at 1433 cm−1 in CCDs was obviously increased because the abundant amino groups of CN-dots reacted with carboxylic acid groups of the CP[5] macrocycles. Powder X-ray diffraction (PXRD) patterns (Figure 1e) of CCDs show the characteristic peaks of CN-dots and CP[5], further

Mechanochemical amorphization of chitin: impact of apparatus material on performance and contamination

• Thomas Di Nardo and
• Audrey Moores

Beilstein J. Org. Chem. 2019, 15, 1217–1225, doi:10.3762/bjoc.15.119

• size and mass, while concentration on amorphization performance, measured by powder X-ray diffraction (PXRD). We selected for this study reaction jars made of copper, aluminum, brass, tungsten carbide, zirconia, stainless steel, PTFE, or poly(methyl methacrylate) (PMMA) paired with one ball of the same

• of polysaccharides In a typical experiment, 200 mg of polysaccharide, chitin was placed in a jar equipped with one ball and milled in a MM 400 mixer mill for 30 min at 29.5 Hz. The resulting powder was used as is for analysis. Powder X-ray diffraction (PXRD) Sample diffractogram was recorded from 5

Insertion of [1.1.1]propellane into aromatic disulfides

• Robin M. Bär,
• Gregor Heinrich,
• Martin Nieger,
• Olaf Fuhr and
• Stefan Bräse

Beilstein J. Org. Chem. 2019, 15, 1172–1180, doi:10.3762/bjoc.15.114

• in most cases. Single crystal X-ray diffraction analysis confirms the rod-like structure of the [2]staffanes that is often required in material applications. Keywords: bicyclo[1.1.1]pentane; bioisosteres; disulfides; linkers; [1.1.1]propellane; Introduction Rigid structures are emerging in both

• [10] and Szeimies et al. obtained 63% of 6a and 27% of 11a [27]. Halogen substitutions were tolerated as well as methyl and methoxy groups. All products of substituted aromatic disulfides are previously unreported. The analysis of compound 6a by single-crystal X-ray diffraction [29] revealed a

• obtain single-crystals of 14 to confirm the structure by X-ray diffraction (Scheme 4) [31]. The rod-like structure of the [2]staffane unit now becomes more tangible. The distance in one BCP unit equals 1.857(3) Å (C1–C5) and the two units are 1.491(4) Å apart from each other (C1–C1’). Reaction with

Mechanochemical synthesis of hyper-crosslinked polymers: influences on their pore structure and adsorption behaviour for organic vapors

• Sven Grätz,
• Sebastian Zink,
• Hanna Kraffczyk,
• Marcus Rose and
• Lars Borchardt

Beilstein J. Org. Chem. 2019, 15, 1154–1161, doi:10.3762/bjoc.15.112

• protocol the polymer obtained through this mechanochemical route is also amorphous as visualized by the XRD (X-ray diffraction) patters recorded (Supporting Information File 1, Figure S1) [43]. Furthermore, NG-HCP similarly shows a high thermal stability with a decomposition onset in air (Supporting

• utilized and the resulting spectra were treated with ATR-correction by the OPUS 6.5 software. Powder X-ray diffraction (PXRD) patterns were collected in transmission geometry (MYTHEN 1K detector) with a STOE STADI P diffractometer operated at 40 kV and 30 mA with a Ge monochromator using Cu Kα1 radiation

Unexpected polymorphism during a catalyzed mechanochemical Knoevenagel condensation

• Sebastian Haferkamp,
• Andrea Paul,
• Adam A. L. Michalchuk and
• Franziska Emmerling

Beilstein J. Org. Chem. 2019, 15, 1141–1148, doi:10.3762/bjoc.15.110

• situ and in real-time by tandem synchrotron powder X-ray diffraction and Raman spectroscopy. For synthesis of p-fluorobenzylidene malonodinitrile (3a) the reaction product crystallizes according to two different pathways, depending on the concentration of base catalyst. At high concentrations of

Novel (2-amino-4-arylimidazolyl)propanoic acids and pyrrolo[1,2-c]imidazoles via the domino reactions of 2-amino-4-arylimidazoles with carbonyl and methylene active compounds

• Victoria V. Lipson,
• Tetiana L. Pavlovska,
• Nataliya V. Svetlichnaya,
• Anna A. Poryvai,
• Nikolay Yu. Gorobets,
• Erik V. Van der Eycken,
• Irina S. Konovalova,
• Svetlana V. Shiskina,
• Alexander V. Borisov,
• Vladimir I. Musatov and
• Alexander V. Mazepa

Beilstein J. Org. Chem. 2019, 15, 1032–1045, doi:10.3762/bjoc.15.101

• the intense signals that occur due to cleavage of the CF3COO− anion. Single crystal X-ray diffraction analysis of biphenyl compound 9i has finally proved the structures of the obtained products (Figure 3). Compound 9i exists as organic salt with trifluoroacetic acid in the crystal phase. The existence

• signals of the ABX protons of the propionyl fragment – СНХ at 4.60–4.30 ppm and СН2АВ at 3.00–2.60 ppm. Finally, the structure of acids 11 was confirmed by X-ray diffraction data of the sample compound 11b (Figure 4). Compound 11b was found to be a zwitterion and exists as monohydrate in the crystal phase

• allows to classify them as compounds of the same type containing a fused aminoimidazo[1,2-c]pyrrole moiety. Finally, the structure of azomethines 16 was confirmed by X-ray diffraction data of the sample compound 16a (Figure 5). All atoms of the bicyclic fragment lie in the plane within 0.01 Å. The

Halogen bonding and host–guest chemistry between N-alkylammonium resorcinarene halides, diiodoperfluorobutane and neutral guests

• Fangfang Pan,
• Mohadeseh Dashti,
• Michael R. Reynolds,
• Kari Rissanen,
• John F. Trant and
• Ngong Kodiah Beyeh

Beilstein J. Org. Chem. 2019, 15, 947–954, doi:10.3762/bjoc.15.91

• interactions to be used in aqueous or polar environments where HB-based systems are less viable [8][9][10][11][12]. However, we lack the analytical tools to directly examine and determine the precise structure of XB assemblies in solution [13][14][15]. In the solid-state, X-ray diffraction has proven an

• crystallography: MeOH-MeCN@1&DIOFB and Water@2&DIOFB. These two structures, besides illustrating the potential of halogen bonding for organizing complex capsular systems, shed light on the importance of flexibility in affecting the self-assembled systems. Results and Discussion Single crystal X-ray diffraction

An anomalous addition of chlorosulfonyl isocyanate to a carbonyl group: the synthesis of ((3aS,7aR,E)-2-ethyl-3-oxo-2,3,3a,4,7,7a-hexahydro-1H-isoindol-1-ylidene)sulfamoyl chloride

• Aytekin Köse,
• Aslı Ünal,
• Ertan Şahin,
• Uğur Bozkaya and
• Yunus Kara

Beilstein J. Org. Chem. 2019, 15, 931–936, doi:10.3762/bjoc.15.89

• sulfamoyl chloride 10. Mechanism for the formation of ylidenesulfamoyl chloride 10. Supporting Information Supporting Information File 450: Theoretical computations, experimental procedures, copies of 1H and 13C NMR spectra, X-ray diffraction and HRMS analysis. Acknowledgements The authors are indebted to