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

• ). Molecular structure of compound 3a (ORTEP plot with 50% probability level). Molecular structure of compound 4b (ORTEP plot with 50% probability level). Superimposition fit of the two conformers, which exist in the ratio of 1:1 in the solid state structure of compound 4b (label A marks the atoms 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

• solid-state structure of 9 displayed a slightly distorted T-shape geometry around the palladium center. A short Pd1–B1 distance of 2.243(2) Å (cf. complex 2: 2.194(3) Å) and a significant pyramidalization at the boron center (ΣBα = 341°) is observed, indicating a strong Pd(0)→B bond. The distance

Methylpalladium complexes with pyrimidine-functionalized N-heterocyclic carbene ligands

• Dirk Meyer and
• Thomas Strassner

Beilstein J. Org. Chem. 2016, 12, 1557–1565, doi:10.3762/bjoc.12.150

• complexes were fully characterized by standard methods and in three cases also by a solid state structure. Keywords: alkane activation; alkyl complex; NHC; palladium; solid state structure; Introduction Palladium complexes have been shown to be versatile homogeneous catalysts in a variety of reactions [1

• ). We could also confirm the formation of the desired product by a solid state structure (Figure 4). Typical reaction conditions of the catalytic CH activation are 30 atmospheres of methane under strongly oxidizing conditions (potassium peroxodisulfate, trifluoroacetic acid and its anhydride), where

• analysis. All energies reported are Gibbs free energies at standard conditions (T = 298 K, p = 1 atm) using unscaled frequencies. For visualization GaussView [75] was used. Solid-state structure determination of 9, 12 and 13 Preliminary examination and data collection were carried out on an area detecting

Stereodynamic tetrahydrobiisoindole “NU-BIPHEP(O)”s: functionalization, rotational barriers and non-covalent interactions

• Golo Storch,
• Sebastian Pallmann,
• Frank Rominger and
• Oliver Trapp

Beilstein J. Org. Chem. 2016, 12, 1453–1458, doi:10.3762/bjoc.12.141

• . Significant signal splitting was observed for both “NU-BIPHEP(O)s” due to strong non-covalent interactions. However, detailed analysis of 3 was hampered due to overlaying multiple signal sets caused by E/Z isomerism of the tertiary amide unit. Adding 4 to a solution of 1b (Figure 3A, solid-state structure) in

• phase for seven days. Investigation of “NU-BIPHEP(O)” 1b. A) Solid-state structure determined by X-ray crystallography. Hydrogen atoms and methanol solvent molecules are omitted for clarity. B) Interaction studies in solution with soluble Okamoto phase 4 by 31P{1H} NMR spectroscopy. Black: spectrum of

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

• the Rh(III) and Ir(III) complexes of 2a, respectively). The structures of [2a-Cp*IrI]BF4, and [5-Cp*IrI]BF4 were confirmed unambiguously by single-crystal X-ray diffraction. The solid-state structure of [2a-Cp*IrI]BF4 confirms the tetrahedral environment of the iridium center, rendering the two faces

Effective in silico prediction of new oxazolidinone antibiotics: force field simulations of the antibiotic–ribosome complex supervised by experiment and electronic structure methods

• Jörg Grunenberg and
• Giuseppe Licari

Beilstein J. Org. Chem. 2016, 12, 415–428, doi:10.3762/bjoc.12.45

• conformational change during the Monte Carlo scan. While in the solid state structure from Haloarcula marismortui this nucleobase is oriented away from linezolid, due to our simulation the nucleobase approaches linezolid interacting through a new H-bond (relaxed force constant: of 0.23 N/cm) between the NH2

Enabling technologies and green processes in cyclodextrin chemistry

• Giancarlo Cravotto,
• Marina Caporaso,
• Laszlo Jicsinszky and
• Katia Martina

Beilstein J. Org. Chem. 2016, 12, 278–294, doi:10.3762/bjoc.12.30

• structure-dependent behaviour, which can be either favourable or unfavourable, because of the solid-state structure. Although BM reactions are often said to be solvent-free, some inert solvents can also be used particularly when the reagent mass ratio is very high. A lack of solvent(s) may suggest that ball

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

• them according to their influence on the solid-state structure, we began investigating alternative measures of intermolecular interactions. We hypothesized that gelation might instead depend on the strength of intermolecular interactions in the solid state. To test this hypothesis, graduate student

Simple activation by acid of latent Ru-NHC-based metathesis initiators bearing 8-quinolinolate co-ligands

• Julia Wappel,
• Roland C. Fischer,
• Luigi Cavallo,
• Christian Slugovc and
• Albert Poater

Beilstein J. Org. Chem. 2016, 12, 154–165, doi:10.3762/bjoc.12.17

• two products, 2a and 2b, were isolated. In this case both complexes featured, according to NMR analysis, two 5,7-dichloro-8-quinolinolate ligands. The overall yield amounted to 83% in this case. Single crystal X-ray structure analyses elucidated the solid state structure of 2a and 2b (see Figure 1

• calculations. Solid state structure of complexes 2a and 2b as retrieved from single crystal X-ray diffraction. Time/conversion plot for the polymerization of 5 by preinitiators 1–4 in the presence of HCl ([5]:[HCl]:[I] = 50:25:1; [5] = 0.1 mol/L; solvent:CDCl3). 1H NMR spectrum in the low-field region of the

A journey in bioinspired supramolecular chemistry: from molecular tweezers to small molecules that target myotonic dystrophy

• Steven C. Zimmerman

Beilstein J. Org. Chem. 2016, 12, 125–138, doi:10.3762/bjoc.12.14

• cleft was not only a significant synthetic challenge, I questioned whether the group might not distort the spacer, thereby altering its dimensions. I was able to prepare small quantities (<100 mg) of 6 and 7 and crystallize both for X-ray analysis (Figure 4) [16]. The solid state structure of 6 revealed

Latent ruthenium–indenylidene catalysts bearing a N-heterocyclic carbene and a bidentate picolinate ligand

• Thibault E. Schmid,
• Florian Modicom,
• Adrien Dumas,
• Etienne Borré,
• Loic Toupet,
• Olivier Baslé and
• Marc Mauduit

Beilstein J. Org. Chem. 2015, 11, 1541–1546, doi:10.3762/bjoc.11.169

• by HCl addition. The versatility of the catalyst was subsequently demonstrated in RCM, CM and enyne metathesis reactions. Solid-state structure of complex 4a from single crystal X-ray diffraction. Hydrogens have been omitted for clarity. (N in blue, C in grey, O in red, Cl in green). Olefin

Surprisingly facile CO₂ insertion into cobalt alkoxide bonds: A theoretical investigation

• Willem K. Offermans,
• Claudia Bizzarri,
• Walter Leitner and
• Thomas E. Müller

Beilstein J. Org. Chem. 2015, 11, 1340–1351, doi:10.3762/bjoc.11.144

• crystal solid-state structure reported for [CoIII(salen)(dinitrophenolate)] [49]. The distance between cobalt and the oxygen atom of the alkoxide chain was 1.9–1.94 Å, with a small yet systematic variation in dependence on the nucleophilicity of L. The more nucleophilic L was, the longer the Co–OR

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

• that the chemical nature of compound 25 has nevertheless been qualitatively confirmed. The spectroscopic data of 25 (see Supporting Information File 1) are consistent with its solid state structure. There are several plausible mechanisms that would explain the formation of 25. This bis-bromine adduct

• solid state structure of 43 was determined by crystal structure analysis. The structure of this adduct is in many ways similar to that of the related PTAD-adduct 37. The ring conformation is again a "sofa", whereby C26 lies 0.7 Å out of the plane of the other five atoms (Figure 5). The angles at C2 and

Donor–acceptor type co-crystals of arylthio-substituted tetrathiafulvalenes and fullerenes

• Xiaofeng Lu,
• Jibin Sun,
• Shangxi Zhang,
• Longfei Ma,
• Lei Liu,
• Hui Qi,
• Yongliang Shao and
• Xiangfeng Shao

Beilstein J. Org. Chem. 2015, 11, 1043–1051, doi:10.3762/bjoc.11.117

• with C60/C70, we have carried out the preparation a series of [(Ar-S-TTF)–(fullerene)] co-crystals and investigated their solid state structure, as reported herein. In this report we focus on the synthesis, composition (donor:acceptor ratio), and crystal structure of the resulting co-crystals. Results

Tuning the size of a redox-active tetrathiafulvalene-based self-assembled ring

• Sébastien Bivaud,
• Sébastien Goeb,
• Vincent Croué,
• Magali Allain,
• Flavia Pop and
• Marc Sallé

Beilstein J. Org. Chem. 2015, 11, 966–971, doi:10.3762/bjoc.11.108

• +, [M6L3-8TfO−]4+, [M6L3-7TfO−]5+ species and matching perfectly with theoretical ones (Supporting Information File 1, Figure S8). Single crystals of assembly M6L3 were grown by slow diffusion of ethyl acetate in DMSO and allowed for determining unambiguously the solid-state structure by a synchrotron X

The preparation of new functionalized [2.2]paracyclophane derivatives with N-containing functional groups

• Henning Hopf,
• Swaminathan Vijay Narayanan and
• Peter G. Jones

Beilstein J. Org. Chem. 2015, 11, 437–445, doi:10.3762/bjoc.11.50

• characterized by their spectroscopic data (Supporting Information File 1), and for 22 we could additionally determine the solid-state structure by X-ray structural analysis (Figure 4a). The orientation of the side chains in 22 is described by the torsion angles C14–C15–N1–C17 131.2(2)°, C15–N1–C17–O −1.3(2

• product was three times as much, we assume that much of the material is lost during chromatography on silica gel. The compound was characterized by its spectroscopic and analytical data and also by the determination of its solid state structure by X-ray diffraction [30]. The molecule of 28 (Figure 6a

A one-pot multistep cyclization yielding thiadiazoloimidazole derivatives

• Debabrata Samanta,
• Anup Rana,
• Jan W. Bats and
• Michael Schmittel

Beilstein J. Org. Chem. 2014, 10, 2989–2996, doi:10.3762/bjoc.10.317

• , 129.0, 141.9, 149.0, 157.1 ppm; anal. calcd for C20H26N4S: C, 67.76; H, 7.39; N, 15.80; S, 9.04; found: C, 67.85; H, 7.54; N, 15.50; S, 9.05. (a) and (b) representing the solid state structure of 2a with displacement ellipsoids at the 50% probability level. Distances are given in black (unit: Å) and

Derivatives of the triaminoguanidinium ion, 3. Multiple N-functionalization of the triaminoguanidinium ion with isocyanates and isothiocyanates

• Jan Szabo,
• Kerstin Karger,
• Nicolas Bucher and
• Gerhard Maas

Beilstein J. Org. Chem. 2014, 10, 2255–2262, doi:10.3762/bjoc.10.234

• biological activity studies, and in crystal engineering. Solid-state structure of 7a·3CH3CN. Left: Molecular structure with numbering of atoms. Right: N–H···Cl, N–H···N(acetonitrile) and N–H···O hydrogen bonds. Thermal displacement ellipsoids are drawn at the 30% probability level. Selected bond lengths (Å

• ): C1–N1 1.330(3), C1–N4 1.333(3), C1–N7 1.332(3), N1–N2 1.397(3), N4–N5 1.388(3), N7–N8 1.401(3). Selected bond angles (°): N1–C1–N4 119.0(2), N1–C1–N7 120.7(2), N4–C1–N7 120.3(2). For torsion angles and hydrogen bonds, see Table 1 and Table S4 (Supporting Information File 1). Solid-state structure of

• -state structure of 10b. Thermal displacement ellipsoids are drawn at the 30% probability level. Selected bond lengths (Å): C2–S1 1.664(2), C2–N4 1.346(3), C2–N5 1.382(3), N3–N4 1.381(3), C1–N1 1.388(3), C1–N3 1.298(2), C1–N5 1.374(2), C23–S2 1.672(2), C23–N2 1.377(2), C23–N7 1.353(3). Hydrogen bonds: a

Scalable synthesis of 5,11-diethynylated indeno[1,2-b]fluorene-6,12-diones and exploration of their solid state packing

• Bradley D. Rose,
• Peter J. Santa Maria,
• Aaron G. Fix,
• Chris L. Vonnegut,
• Lev N. Zakharov,
• Sean R. Parkin and
• Michael M. Haley

Beilstein J. Org. Chem. 2014, 10, 2122–2130, doi:10.3762/bjoc.10.219

• utilized 3 – while the solid-state structure of 3 showed several sub-van der Waals contact distances, the n-type mobility of the OFET was very low (2 × 10−5 cm2 V−1 s−1) [14]. On the other hand, an OFET utilizing 4 (X = F) had measured electron mobilities of 0.17 cm2 V−1 s−1, and its X-ray crystal

Five-membered ring annelation in [2.2]paracyclophanes by aldol condensation

• Henning Hopf,
• Swaminathan Vijay Narayanan and
• Peter G. Jones

Beilstein J. Org. Chem. 2014, 10, 2021–2026, doi:10.3762/bjoc.10.210

• difference that the preferred endo-conformation has been observed both for the solid state [8][9][10] and in solution by NMR spectroscopy [11]. We hence assume that the conformation of 9 in solution resembles that of the solid state structure given in Scheme 2. With this assumption we can easily rationalize

Aryl substitution of pentacenes

• Andreas R. Waterloo,
• Anna-Chiara Sale,
• Dan Lehnherr,
• Frank Hampel and
• Rik R. Tykwinski

Beilstein J. Org. Chem. 2014, 10, 1692–1705, doi:10.3762/bjoc.10.178

• ; pentacene; π-stacking; polycyclic aromatic hydrocarbon; solid-state structure; Introduction Conjugated organic molecules are promising candidates for use in optoelectronic applications including OLEDs [1], photovoltaics [2], and OFETs [3]. Even though there is literally an infinite number of possibilities

• crystallizes in the space group C2/c with eight molecules in the unit cell (Figure 5). Within the solid-state structure, the pendant phenyl ring and the pentacene core are slightly twisted, with a torsion angle of ~71°. Molecules of pentacene 3a arrange as dimeric pairs, which then pack into a so-called

The difluoromethylene (CF₂) group in aliphatic chains: Synthesis and conformational preference of palmitic acids and nonadecane containing CF₂ groups

• Yi Wang,
• Ricardo Callejo,
• Alexandra M. Z. Slawin and
• David O’Hagan

Beilstein J. Org. Chem. 2014, 10, 18–25, doi:10.3762/bjoc.10.4

• two other analogues 6a and 6b, and also of palmitic acid itself. The solid state structure of 6c and 27 show that the 1,4-di-CF2 motif prefers an anti-zig-zag conformation. We attribute this preference to intramolecular dipole–dipole relaxation which is maximised in the extended anti-zig-zag chain

Studies on the interaction of isocyanides with imines: reaction scope and mechanistic variations

• Ouldouz Ghashghaei,
• Consiglia Annamaria Manna,
• Esther Vicente-García,
• Marc Revés and
• Rodolfo Lavilla

Beilstein J. Org. Chem. 2014, 10, 12–17, doi:10.3762/bjoc.10.3

• monocrystal of the bis(imino)azetidine 3a was subjected to X-ray diffraction analysis and the solid state structure is depicted in Figure 1 [11]. This result confirms the structural features associated to this scaffold, and also raises some questions on the origin of the stereochemistry associated to the C=N

Dipolar addition to cyclic vinyl sulfones leading to dual conformation tricycles

• Steven S. Y. Wong,
• Michael G. Brant,
• Christopher Barr,
• Allen G. Oliver and
• Jeremy E. Wulff

Beilstein J. Org. Chem. 2013, 9, 1419–1425, doi:10.3762/bjoc.9.159

• /mol). The calculated structure of the lower-energy exo conformer was similar to the solid-state structure shown in Figure 1, and was consistent with the nOe and NMR shielding data discussed above. Seeking further evidence linking the calculated exo and endo structures to the observed major and minor

Host–guest complexes of mixed glycol-bipyridine cryptands: prediction of ion selectivity by quantum chemical calculations, part V

• Svetlana Begel,
• Ralph Puchta and
• Rudi van Eldik

Beilstein J. Org. Chem. 2013, 9, 1252–1268, doi:10.3762/bjoc.9.142

• 2.2.bpy]Br and the (B3LYP/LANL2DZp) calculated C2 symmetric [Na 2.2.bpy]+-ion. The bonds between the sodium cation and the donor atoms are around 5.5% longer than in the averaged solid-state structure (Table 1). Whereas Table 1 and Table 2 present significant data for all discussed structures, Figure

• Na+, but the solid-state structure of [Na 2.2.bpy]Br is somehow distorted (X-ray: C1 symmetry compared to calculated C2) [61], to allow the cationic sodium center to interact with the available cryptand donor atoms and to get a better stabilization as in the applied weakly coordinating solvent