cis-Diastereoselective synthesis of chroman-fused tetralins as B-ring-modified analogues of brazilin

• Dimpee Gogoi,
• Runjun Devi,
• Pallab Pahari,
• Bipul Sarma and
• Sajal Kumar Das

Beilstein J. Org. Chem. 2016, 12, 2816–2822, doi:10.3762/bjoc.12.280

• evidences for the structural assignment were sought from X-ray crystallography. Fortunately, we got the single crystals of (±)-5k by slow evaporation of a solution of 5k in hexane/EtOAc, and its molecular structure was confirmed by X-ray diffraction analysis (Figure 3). The 1H and 13C NMR spectra of all the

From betaines to anionic N-heterocyclic carbenes. Borane, gold, rhodium, and nickel complexes starting from an imidazoliumphenolate and its carbene tautomer

• Ming Liu,
• Jan C. Namyslo,
• Martin Nieger,
• Mika Polamo and
• Andreas Schmidt

Beilstein J. Org. Chem. 2016, 12, 2673–2681, doi:10.3762/bjoc.12.264

• of the carbene atom appears at δ = 183.9 ppm. Single crystals of the gold complex 9 were obtained by slow evaporation of a concentrated solution of 9 in MeOH and a molecular drawing is shown in Figure 3. The X-ray structure revealed a mixed occupation of the same position with chloride and bromide

• ), 6.72 ppm, and 5.81 ppm, respectively. Single crystals of [Rh(7)3] (11) were obtained by slow evaporation of a concentrated solution of 11 in a mixture of EtOAc and MeOH. The single crystal X-ray analysis proved that three anionic N-heterocyclic carbenes 7 serve as bidentate ligands, respectively

• ) chloride at reflux temperature resulted in the formation of the nickel complex [Ni(7)2] (12, Scheme 2). Single crystals were obtained by slow evaporation of 12 from EtOAc/MeOH. The X-ray analysis shows two independent nickel complexes which are connected via hydrogen bonds to two water molecules (Figure 5

Effects of solvent additive on “s-shaped” curves in solution-processed small molecule solar cells

• John A. Love,
• Shu-Hua Chou,
• Ye Huang,
• Guilllermo C. Bazan and
• Thuc-Quyen Nguyen

Beilstein J. Org. Chem. 2016, 12, 2543–2555, doi:10.3762/bjoc.12.249

• . While attempts to grow single crystals of this material have thus far been unsuccessful and thus the peaks cannot be indexed precisely, by convention we attribute this spacing to an “alkyl stacking peak”, that is a spacing arising from molecules separated by alkyl chains analogous to the lamellae

Radical polymerization by a supramolecular catalyst: cyclodextrin with a RAFT reagent

• Kohei Koyanagi,
• Yoshinori Takashima,
• Takashi Nakamura,
• Hiroyasu Yamaguchi and
• Akira Harada

Beilstein J. Org. Chem. 2016, 12, 2495–2502, doi:10.3762/bjoc.12.244

• to studying the polymerization of vinyl monomers, we investigated the complex formation of CDs with vinyl monomers. When mixing α-CD and DMA, we obtained single crystals suitable for X-ray crystallography analysis. The X-ray crystallography analysis is important to understand the complex in the

Synthesis, dynamic NMR characterization and XRD studies of novel N,N’-substituted piperazines for bioorthogonal labeling

• Constantin Mamat,
• Marc Pretze,
• Matthew Gott and
• Martin Köckerling

Beilstein J. Org. Chem. 2016, 12, 2478–2489, doi:10.3762/bjoc.12.242

• observed for all nitro derivatives due to the limited change of the piperazine chair conformation. Therefore, two coalescence points were determined and their resulting activation energy barriers were calculated using 1H NMR. To support this result, single crystals of 1-(4-nitrobenzoyl)piperazine (3a

• showed a Tc of 248 K with a ΔG# of 11.1 kJ/mol [23] whereas piperidine shows a higher ΔG# of 42.3 and N-methylpiperidine a ΔG# = 49.8 kJ/mol [21][28]. X-ray structure analyses of 3a and 4b Single crystals of 3a and 4b were obtained and their molecular structures determined using single crystal X-ray

Synthesis and characterization of fluorinated azadipyrromethene complexes as acceptors for organic photovoltaics

• Forrest S. Etheridge,
• Roshan J. Fernando,
• Sandra Pejić,
• Matthias Zeller and
• Geneviève Sauvé

Beilstein J. Org. Chem. 2016, 12, 1925–1938, doi:10.3762/bjoc.12.182

• and L3 chelates. The estimated HOMO and LUMO energy levels obtained from cyclic voltammetry are shown in Figure 8. The HOMO and LUMO of Zn(L1)2 and Zn(L4)2 approach those of PCBM. Crystallography Single crystals of the zinc(II) chelates were grown in order to better understand the structure of the

A T-shape diphosphinoborane palladium(0) complex

• Patrick Steinhoff and
• Michael E. Tauchert

Beilstein J. Org. Chem. 2016, 12, 1573–1576, doi:10.3762/bjoc.12.152

• the ligand pointing towards the formation of a bisligand complex (DPB)2Pd [7]. Unlike complex 2 we were unable to form a pyridine adduct complex by treatment of 9 with 10 equiv of pyridine. Single crystals of complex 9 suitable for X-ray diffraction analysis were grown from hexane (Figure 2). The

Dinuclear thiazolylidene copper complex as highly active catalyst for azid–alkyne cycloadditions

• Anne L. Schöffler,
• Ata Makarem,
• Frank Rominger and
• Bernd F. Straub

Beilstein J. Org. Chem. 2016, 12, 1566–1572, doi:10.3762/bjoc.12.151

• vacuo to give the colourless product 1b (1.50 g, 2.75 mmol, 76%). Single crystals of salt 1b that were suitable for an X-ray structure analysis were obtained from acetone/diethyl ether. 1H NMR (400.33 MHz, acetone-d6, 295.0 K) δ 9.88 (s, 2H, NCHS), 5.42 (s, 4H, CH2), 2.68 (s, 6H, NCCH3), 2.66 (s, 6H

Antibacterial structure–activity relationship studies of several tricyclic sulfur-containing flavonoids

• Lucian G. Bahrin,
• Henning Hopf,
• Peter G. Jones,
• Laura G. Sarbu,
• Cornelia Babii,
• Alina C. Mihai,
• Marius Stefan and
• Lucian M. Birsa

Beilstein J. Org. Chem. 2016, 12, 1065–1071, doi:10.3762/bjoc.12.100

• new broad absorption band at around 1040 cm−1 is attributed to the tetrafluoroborate anion. ESIMS confirms the structure of the positive molecular fragment of each tricyclic flavonoid ([M − BF4]+). Single crystals suitable for X-ray analysis were obtained for 5a and 5b and the results are presented in

Bi- and trinuclear copper(I) complexes of 1,2,3-triazole-tethered NHC ligands: synthesis, structure, and catalytic properties

• Shaojin Gu,
• Jiehao Du,
• Jingjing Huang,
• Huan Xia,
• Ling Yang,
• Weilin Xu and
• Chunxin Lu

Beilstein J. Org. Chem. 2016, 12, 863–873, doi:10.3762/bjoc.12.85

• range of 157.6–216 ppm [34][35]. Single crystal X-ray diffraction studies To obtain additional insight into the coordination and supramolecular properties, suitable single crystals of all the copper complexes were obtained for single-crystal X-ray diffraction analysis. Crystals were grown by slow

• diffusion of diethyl ether into an acetonitrile solution of the copper complex at room temperature. Green-yellow single crystals of complex 2 suitable for an X-ray diffraction study were grown from acetonitrile solution and diethyl ether. The molecular structure of complex 2 in the solid state is depicted

• environment of two nitrogen atoms and two oxyen atoms. The Cu–O bonds are in trans configuration and Cu–O distances are shorter than Cu–N distances. The two ligands are arranged in head-to-tail manner. And the Ntriazole did not participate in the corrdination. Single crystals of complex 3 suitable for an X

A modular approach to neutral P,N-ligands: synthesis and coordination chemistry

• Vladislav Vasilenko,
• Torsten Roth,
• Clemens K. Blasius,
• Sebastian N. Intorp,
• Hubert Wadepohl and
• Lutz H. Gade

Beilstein J. Org. Chem. 2016, 12, 846–853, doi:10.3762/bjoc.12.83

• 7 were prepared. It should be noted that ligands 2, 5, and 7 feature a distinct shift of the 31P NMR resonance to lower fields upon complexation of a rhodium(I) or iridium(I) center, whereas a shift to higher fields is observed for ligand 3 [11]. We were able to obtain single crystals of compounds

• residue was filtered off and the filtrate was layered with toluene and pentane, and stored at −40 °C. This procedure yielded a powder or in several cases single crystals suitable for X-ray diffraction. The solid was then washed with pentane and dried under high vacuum for several days to remove residual

• cationic palladium species [2a-PdCl]BF4, which is dimeric in the solid state [11]. Similarly, Pd(allyl) complexes of ligands 2a, 5 and 7 were obtained from mixtures of the respective ligand, [Pd(allyl)Cl]2 and AgBF4 or AgOTf as the chloride scavenger in DCM (Figure 5B). We were able to obtain single

My maize and blue brick road to physical organic chemistry in materials

• Anne J. McNeil

Beilstein J. Org. Chem. 2016, 12, 229–238, doi:10.3762/bjoc.12.24

• just three compounds before gelator 2b was discovered. Single crystals of 2b revealed a surprising 1D π-stacking interaction, rather than the expected cation–π interaction. Nevertheless, powder X-ray diffraction (PXRD) analysis revealed that the packing within the single crystal was not representative

• single crystals of six gelators and five nongelators. Of the six gelator crystal structures, only three had PXRD patterns that matched the gel. Within this limited data set we found 1D intermolecular interactions being present and absent amongst both gelators and nongelators, providing no clear

Inclusion complexes of 2-methoxyestradiol with dimethylated and permethylated β-cyclodextrins: models for cyclodextrin–steroid interaction

• Mino R. Caira,
• Susan A. Bourne,
• Halima Samsodien and
• Vincent J. Smith

Beilstein J. Org. Chem. 2015, 11, 2616–2630, doi:10.3762/bjoc.11.281

• employed for preliminary investigation of single crystals of a putative inclusion complex between 2ME and DIMEB, prepared using the co-precipitation method. (Details of the thermal analysis of the DIMEB complex of 2ME are provided in the Supporting Information File 1). The crystals, immersed in silicone

• , single crystals of the putative DIMEB complex were dissolved in a MeOH/water medium and UV spectrophotometric analysis yielded a host–guest ratio of 1:1. Together with the TGA estimate of water content (5.3 ± 0.3%, n = 3), the complex formula DIMEB·2ME·(5.5 ± 0.3)H2O was indicated. A putative inclusion

• indicated from UV spectrophotometric measurements of a solution of dissolved single crystals. Definitive structural information for crystalline inclusion complexes between 2ME and the hosts DIMEB and TRIMEB Since the unit cell dimensions of the two inclusion complexes had no counterparts in the Cambridge

Supramolecular chemistry: from aromatic foldamers to solution-phase supramolecular organic frameworks

• Zhan-Ting Li

Beilstein J. Org. Chem. 2015, 11, 2057–2071, doi:10.3762/bjoc.11.222

• Li+. Solution-phase supramolecular metal–organic frameworks (MOFs) Periodicity is the key feature of single crystals in which molecules arrange repeatedly in the three-dimensional space. Porous crystals such as metal–organic frameworks (MOFs) exhibit many unique properties mainly due to their large

New aryloxybenzylidene ruthenium chelates – synthesis, reactivity and catalytic performance in ROMP

• Patrycja Żak,
• Szymon Rogalski,
• Mariusz Majchrzak,
• Maciej Kubicki and
• Cezary Pietraszuk

Beilstein J. Org. Chem. 2015, 11, 1910–1916, doi:10.3762/bjoc.11.206

• of CuCl at 60 °C. After 24 h of the reaction course, the formation of a green precipitate was observed. X-ray diffraction analysis of single crystals obtained by slow evaporation of the post-reaction mixture revealed the formation of dimeric complex 16, in which the phenoxybenzylidene ring was

Synthesis and structures of ruthenium–NHC complexes and their catalysis in hydrogen transfer reaction

• Chao Chen,
• Chunxin Lu,
• Qing Zheng,
• Shengliang Ni,
• Min Zhang and
• Wanzhi Chen

Beilstein J. Org. Chem. 2015, 11, 1786–1795, doi:10.3762/bjoc.11.194

• and 2 are stable in air and under light irradiation. Single crystals suitable for X-ray diffraction could be obtained by slow diffusion of Et2O into CH3CN solutions and the detailed structure of 1 is depicted in Figure 1. In complex 1, the central ruthenium ion is hexacoordinated by two bidentate NHC

Star-shaped tetrathiafulvalene oligomers towards the construction of conducting supramolecular assembly

• Masahiko Iyoda and
• Masashi Hasegawa

Beilstein J. Org. Chem. 2015, 11, 1596–1613, doi:10.3762/bjoc.11.175

• , and particles, amphiphilic TTFs having a rigid core and long alkyl chains are one of the best molecular systems. The self-assembly of TTF derivatives in solid and on surface gives rise to a long-distance dynamic ordering as compared with single crystals. Among the recent researches on TTF and its

• which the three TTF units stack in face-to-face manner to form single crystals (Figure 7). In the case of 23 with butyl chains, this molecule dimerized in CDCl3 solution (K2 = 1.58 ± 0.30 M−1 at 293 K). The chemical shift of the central benzene ring clearly shifted higher field with an increase of

• waves corresponding to the formation of 4410+ and 4420+. Trisubstituted 38 showed polymorphism and formed single crystals from CH2Cl2, whereas it produced a yellow fibrous material from CH2Cl2–hexane 1:4. X-ray diffractometry (XRD) exhibited that fiber 38 possesses a hexagonal columnar structure

Synthesis of racemic and chiral BEDT-TTF derivatives possessing hydroxy groups and their achiral and chiral charge transfer complexes

• Sara J. Krivickas,
• Chiho Hashimoto,
• Junya Yoshida,
• Akira Ueda,
• Kazuyuki Takahashi,
• John D. Wallis and
• Hatsumi Mori

Beilstein J. Org. Chem. 2015, 11, 1561–1569, doi:10.3762/bjoc.11.172

• electode with 0.1 M tetrabutylammonium perchlorate in benzonitrile. These potentials are similar to those of (S,S)- and (R,R)-2 with E11/2, E21/2, and ΔE of 0.52, 0.80, and 0.28 V, respectively. Preparations of single crystals for achiral charge transfer salt θ21-[(S,S)-2]3[(R,R)-2]3(ClO4)2 and chiral

Towards inhibitors of glycosyltransferases: A novel approach to the synthesis of 3-acetamido-3-deoxy-D-psicofuranose derivatives

• Maroš Bella,
• Miroslav Koóš and
• Chun-Hung Lin

Beilstein J. Org. Chem. 2015, 11, 1547–1552, doi:10.3762/bjoc.11.170

• -psicofuranoside derivative 15. X-ray analysis Single crystals (stable at ambient temperature) that were suitable for X-ray diffraction measurements were obtained by slow crystallization of 12 from EtOAc/hexane 1:2 with cooling in a refrigerator. The preliminary orientation matrices and final cell parameters were

Deproto-metallation of N-arylated pyrroles and indoles using a mixed lithium–zinc base and regioselectivity-computed CH acidity relationship

• Mohamed Yacine Ameur Messaoud,
• Ghenia Bentabed-Ababsa,
• Madani Hedidi,
• Aïcha Derdour,
• Floris Chevallier,
• Yury S. Halauko,
• Oleg A. Ivashkevich,
• Vadim E. Matulis,
• Laurent Picot,
• Valérie Thiéry,
• Thierry Roisnel,
• Vincent Dorcet and
• Florence Mongin

Beilstein J. Org. Chem. 2015, 11, 1475–1485, doi:10.3762/bjoc.11.160

• spectrometer at 300 and 75 MHz, respectively. 1H chemical shifts (δ) are given in ppm relative to the solvent residual peak, 13C chemical shifts are relative to the central peak of the solvent signal [55]. Mass spectra measurements were performed using a HP 6890 instrument. Crystallography. The single crystals

Tetrathiafulvalene-based azine ligands for anion and metal cation coordination

• Awatef Ayadi,
• Aziz El Alamy,
• Olivier Alévêque,
• Magali Allain,
• Nabil Zouari,
• Mohammed Bouachrine and
• Abdelkrim El-Ghayoury

Beilstein J. Org. Chem. 2015, 11, 1379–1391, doi:10.3762/bjoc.11.149

• structure refinement are given in Table 1. Crystallographic data for the structural analysis have been deposited within the Cambridge Crystallographic Data Centre, CCDC 1055120 (ligand L1) and CCDC 1055119 (complex 3). Suitable single crystals for X-ray analysis have been grown for ligand L1 upon

• in refluxing toluene, under no light and inert atmosphere, afforded a mononuclear neutral complex 3 described as [ReL2(CO)3Cl]·0.5H2O as a dark precipitate [50]. Single crystals of 3 were obtained by recrystallization from acetone/hexane solution. Details about data collection and structure

• . Single crystals of ligand L1 have been obtained and its crystal structure indicates the ligand is completely planar with the occurrence of a strong intramolecular as well as intermolecular hydrogen bonding. Inorganic anions titration experiments showed that the two ligands are suitable candidates for the

The chemical behavior of terminally tert-butylated polyolefins

• Dagmar Klein,
• Henning Hopf,
• Peter G. Jones,
• Ina Dix and
• Ralf Hänel

Beilstein J. Org. Chem. 2015, 11, 1246–1258, doi:10.3762/bjoc.11.139

• single crystals of this derivative, the assignment of its exact stereostructure (syn- or anti-epoxide) must remain tentative. Since many other epoxidations take place with retention of the original double bond configuration, we assume that the anti-configuration is more probable in the present case as

• stereospecifically, but since we could not obtain single crystals of X-ray quality in this case we refrain from stereochemical assignments (note also that the added heterocycles could in principle be in syn- or anti-orientation). Chemically and stereochemically the situation becomes even more intricate on further

• deuteriochloroform solution in the presence of air, endo-peroxide 52 was isolated in 46% yield. Its structure follows from its spectroscopic data (see Supporting Information File 1) and, in particular, an X-ray structural investigation of single crystals obtained from a petrol ether solution. The molecule of 52 is

Thiazole-induced rigidification in substituted dithieno-tetrathiafulvalene: the effect of planarisation on charge transport properties

• Rupert G. D. Taylor,
• Joseph Cameron,
• Iain A. Wright,
• Neil Thomson,
• Olena Avramchenko,
• Alexander L. Kanibolotsky,
• Anto R. Inigo,
• Tell Tuttle and
• Peter J. Skabara

Beilstein J. Org. Chem. 2015, 11, 1148–1154, doi:10.3762/bjoc.11.129

• functionalisation [3]. This has led to widespread use of TTF-containing compounds in organic photovoltaic (OPV) devices [4][5][6][7] and in organic field effect transistors (OFETs), as both single crystals [8][9] and thin films [10][11] demonstrating charge carrier mobilities of up to 1.2 cm2 V−1 s−1 [2] for single

Regioselective synthesis of chiral dimethyl-bis(ethylenedithio)tetrathiafulvalene sulfones

• Flavia Pop and
• Narcis Avarvari

Beilstein J. Org. Chem. 2015, 11, 1105–1111, doi:10.3762/bjoc.11.124

• elemental analysis, which are all concordant, the definite proof for the sulfone structure of 1 has been provided by single crystal X-ray diffraction analysis. Single crystals of the two enantiomers (S,S)-1 and (R,R)-1 were obtained by slow evaporation from dichloromethane/pentane or dichloromethane

• a yellow orange solid (27 mg, 30%). Single crystals were obtained by slow evaporation of a dichloromethane solution. 1H NMR (500 MHz, CD2Cl2) δ 3.71–3.68 (m, 2H, -SCH2-), 3.56–3.53 (m, 2H, -CH2-S), 3.27–3.21 (m, 2H, S-CH-CH3), 1.42 (d, 6H, -CH3) ppm; 13C NMR (100 MHz, CD2Cl2) δ 136.06, 120.59

• starting from (R,R)-3. Yellow orange solid (32 mg, 35%). Single crystals were obtained by slow evaporation of a dichloromethane solution. Anal. calcd for C12H12O2S8: C, 32.41; H, 2.72; O, 7.19; S, 57.68; found: C, 32.68; H, 2.61; O, 7.01; S, 57.88 (%). Crystallography: X-ray diffraction measurements were

Indolizines and pyrrolo[1,2-c]pyrimidines decorated with a pyrimidine and a pyridine unit respectively

• Marcel Mirel Popa,
• Emilian Georgescu,
• Mino R. Caira,
• Florentina Georgescu,
• Constantin Draghici,
• Raluca Stan,
• Calin Deleanu and
• Florea Dumitrascu

Beilstein J. Org. Chem. 2015, 11, 1079–1088, doi:10.3762/bjoc.11.121

• . For this reason we paid some attention to their structural characterization. To our knowledge the X-ray structures for the parent compounds 6–8 were not reported previously and we thus attempted to obtain suitable single crystals. Only compounds 6 and 8 could be isolated as monocrystals and their X