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

• -crystal X-ray diffraction data were collected at 298(2) K on a Siemens Smart-CCD area-detector diffractometer with a MoKα radiation (λ = 0.71073 Å) by using a ω-2θ scan mode. Unit-cell dimensions were obtained with least-squares refinement. Data collection and reduction were performed using the Oxford

• catalyst solution (0.01 mmol, 0.001 mmol, or 0.0001 mol of ruthenium complexes in iPrOH (1 mL) was injected. Aliquots (0.2 mL) were taken at fixed time intervals, quenched with 1 mL of H2O and extracted with 3 mL of Et2O. The product yields were determined by GC analysis. X-ray diffraction analysis Single

Polythiophene and oligothiophene systems modified by TTF electroactive units for organic electronics

• Alexander L. Kanibolotsky,
• Neil J. Findlay and
• Peter J. Skabara

Beilstein J. Org. Chem. 2015, 11, 1749–1766, doi:10.3762/bjoc.11.191

• CS2 was used for NMR spectroscopy in these cases. For compound 54 (n = 2) the absorption spectrum as a thin film exhibits a maximum at 496 nm and is red-shifted by 35 nm compared to the solution state spectrum, suggesting strong intermolecular interactions in the solid phase. Single crystal X-ray

• diffraction of 54 (n = 2) (Figure 5) revealed that the molecules in the solid state are essentially planar, apart from a significant torsion angle of 33° between the terminal thiophene A and the thiophene B. The angle between planes D and F is 5.79°, with the inter-ring distance being 3.74 Å. The angle

Fe(II)/Et₃N-Relay-catalyzed domino reaction of isoxazoles with imidazolium salts in the synthesis of methyl 4-imidazolylpyrrole-2-carboxylates, its ylide and betaine derivatives

• Ekaterina E. Galenko,
• Olesya A. Tomashenko,
• Alexander F. Khlebnikov,
• Mikhail S. Novikov and
• Taras L. Panikorovskii

Beilstein J. Org. Chem. 2015, 11, 1732–1740, doi:10.3762/bjoc.11.189

• (39.51 ppm). Mass spectra were recorded on a Bruker maXis HRMS–ESI–QTOF, with electrospray ionization in positive mode. IR spectra were recorded on a Bruker FTIR spectrometer Tensor 27 for tablets in KBr, only characteristic absorption is indicated. The single crystal X-ray diffraction experiment was

The facile construction of the phthalazin-1(2H)-one scaffold via copper-mediated C–H(sp²)/C–H(sp) coupling under mild conditions

• Wei Zhu,
• Bao Wang,
• Shengbin Zhou and
• Hong Liu

Beilstein J. Org. Chem. 2015, 11, 1624–1631, doi:10.3762/bjoc.11.177

• , entry 19). In addition, single-crystal X-ray diffraction of 3a showed that the Z-isomer of the alkene is preferentially formed [24]. Next, the scope of 8-aminoquinoline benzamides and the generality of this process were investigated under the optimized conditions. As shown in Scheme 2, most of the

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

Design and synthesis of hybrid cyclophanes containing thiophene and indole units via Grignard reaction, Fischer indolization and ring-closing metathesis as key steps

• Sambasivarao Kotha,
• Ajay Kumar Chinnam and
• Mukesh E. Shirbhate

Beilstein J. Org. Chem. 2015, 11, 1514–1519, doi:10.3762/bjoc.11.165

• unambiguously assigned (δ = 5.63, t, J = 5.40 Hz, 2H). The stereochemistry of the double bond was assigned based on single crystal X-ray diffraction studies and it was found to be the cis (Figure 2) [41]. Having, demonstrated the RCM step, next, we attempted to expand this strategy. In this regard a synthesis

Synthesis of a tricyclic lactam via Beckmann rearrangement and ring-rearrangement metathesis as key steps

• Sambasivarao Kotha,
• Ongolu Ravikumar and
• Jadab Majhi

Beilstein J. Org. Chem. 2015, 11, 1503–1508, doi:10.3762/bjoc.11.163

• towards BR (Scheme 6). The stereostructure of the oxime 11b has been determined by single crystal X-ray diffraction data (Figure 2) [33]. Allylation of lactam 12 in the presence of NaH/allyl bromide in dry DMF gave the allyl derivative 2 in 80% yield. Finally, the RRM of compound 2 was accomplished with G

Consequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivity

• Karolina Żukowska,
• Eva Pump,
• Aleksandra E. Pazio,
• Krzysztof Woźniak,
• Luigi Cavallo and
• Christian Slugovc

Beilstein J. Org. Chem. 2015, 11, 1458–1468, doi:10.3762/bjoc.11.158

• -position changes the thermodynamic equilibrium favoring the trans- over the cis-isomers. In any case, a remarkable thermal stability of all studied compounds was found. Intrigued by the observed phenomenon, we turned to structural studies. Structures of 14 and 15 have been determined using single-crystal X

• -ray diffraction. Each of them includes two molecules of the studied compound in the trans-conformation and one molecule of the solvent (dichloromethane) in the asymmetric part of the unit cell (Figure 2). Both crystals are isotypic, so the crystal packing is identical and lattice dimensions are very

Design and synthesis of polycyclic sulfones via Diels–Alder reaction and ring-rearrangement metathesis as key steps

• Sambasivarao Kotha and
• Rama Gunta

Beilstein J. Org. Chem. 2015, 11, 1373–1378, doi:10.3762/bjoc.11.148

• supported by HRMS data. In addition, the structure and stereochemistry of the allyl groups present in compound 2a have been confirmed by single-crystal X-ray diffraction studies and this data clearly indicated that the allylation had occurred at α-position of the sulfone moiety and the two allyl groups are

Spiro annulation of cage polycycles via Grignard reaction and ring-closing metathesis as key steps

• Sambasivarao Kotha,
• Mohammad Saifuddin,
• Rashid Ali and
• Gaddamedi Sreevani

Beilstein J. Org. Chem. 2015, 11, 1367–1372, doi:10.3762/bjoc.11.147

• ) reaction as a key step is described. The structures of three new cage compounds 7, 12 and 18 were confirmed by single crystal X-ray diffraction studies. Keywords: cage molecules; Diels–Alder reaction; Grignard reaction; ring-closing metathesis; spirocycles; Introduction Design and synthesis of

• 1H and 13C NMR spectral data and further supported by HRMS data. Finally their structures have been unambiguousily established by single crystal X-ray diffraction studies [48] (Figure 3). Since our goal was to synthesize the diallylated compound 11, we screened various reaction conditions and finally

• 7 and 17 have been confirmed by 1H and 13C NMR spectral data and also supported by HRMS data with a molecular weight of 355.16 for 7 and 343.16 for compound 17, respectively. Furthermore, the structure of the bis-spiro pyrano cage compound 7 was confirmed by single crystal X-ray diffraction studies

Selected synthetic strategies to cyclophanes

• Sambasivarao Kotha,
• Mukesh E. Shirbhate and
• Gopalkrushna T. Waghule

Beilstein J. Org. Chem. 2015, 11, 1274–1331, doi:10.3762/bjoc.11.142

• by column chromatography [174]. Moreover, it was observed that cis-sulfone generates the monomeric cyclophane 249 during the metathesis as confirmed by single crystal X-ray diffraction data while the trans-sulfone gave the dimer 252. Finally, the desulfonylation followed by the hydrogenation sequence

Design and synthesis of fused polycycles via Diels–Alder reaction and ring-rearrangement metathesis as key steps

• Sambasivarao Kotha and
• Ongolu Ravikumar

Beilstein J. Org. Chem. 2015, 11, 1259–1264, doi:10.3762/bjoc.11.140

• equivalents of allyl bromide in the presence of an excess amount of NaH to generate the mono-O-allyl compound 5 and surprisingly the di-O-allyl compound was not formed. The stereostructure of 5 has been established on the basis of single-crystal X-ray diffraction studies [29] and it shows the steric hindrance

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

• by single crystal X-ray diffraction. The conformation of the enantiomers is very similar in the solid state, including the equatorial position of the methyl substituents, in spite of their different packing diagrams which are dominated by the intermolecular S···S interactions. The electrochemical

Synthesis and characterization of the cyanobenzene-ethylenedithio-TTF donor

• Sandrina Oliveira,
• Dulce Belo,
• Isabel C. Santos,
• Sandra Rabaça and
• Manuel Almeida

Beilstein J. Org. Chem. 2015, 11, 951–956, doi:10.3762/bjoc.11.106

• -tetrathiafulvalene (CNB-EDT-TTF), was obtained in high yield, by a cross-coupling reaction with triethyl phosphite between 2-thioxobenzo[d][1,3]dithiole-5-carbonitrile and 5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiin-2-one. This new donor was characterized namely by single crystal X-ray diffraction, cyclic

Trifluoromethyl-substituted tetrathiafulvalenes

• Olivier Jeannin,
• Frédéric Barrière and
• Marc Fourmigué

Beilstein J. Org. Chem. 2015, 11, 647–658, doi:10.3762/bjoc.11.73

• functionalized at various positions with the electron-withdrawing –CF3 (trifluoromethyl) group such as EDT-TTF(CF3) (1c) or EDT-TTF(CF3)2 (2cc) (Scheme 2) [31]. Single-crystal X-ray diffraction measurements revealed the recurrent formation of layered structures with a strong segregation of the fluorinated

TTFs nonsymmetrically fused with alkylthiophenic moieties

• Rafaela A. L. Silva,
• Bruno J. C. Vieira,
• Marta M. Andrade,
• Isabel C. Santos,
• Sandra Rabaça,
• Dulce Belo and
• Manuel Almeida

Beilstein J. Org. Chem. 2015, 11, 628–637, doi:10.3762/bjoc.11.71

• /AgCl, typical of TTF donors at E11/2 = 279 V and E21/2 = 680 V for 1 and E11/2 = 304 V and E21/2 = 716 V in the case of 2. The single-crystal X-ray structure of 1 and of a charge transfer salt of 2, (α-mtdt)[Au(mnt)2] (3), are reported. Keywords: cyclic voltammetry; single-crystal X-ray diffraction

Synthesis of dinucleoside acylphosphonites by phosphonodiamidite chemistry and investigation of phosphorus epimerization

• William H. Hersh

Beilstein J. Org. Chem. 2015, 11, 184–191, doi:10.3762/bjoc.11.19

• corresponding acyl diamidites, RC(O)P(N(iPr)2)2 (R = Me (7), Ph (9)), without the intervention of sodium to give a phosphorus anion. The structure of 9 was confirmed by single-crystal X-ray diffraction. The coupling of the diamidites 7 and 9 with 5′-O-DMTr-thymidine was carried out with N-methylimidazolium

• strong carbonyl band in the infrared spectrum at 1631 cm−1. X-ray crystal structure of 9. Large crystals of 9 could be obtained from hexane, allowing confirmation of the structure by single-crystal X-ray diffraction [51]. An ORTEP drawing is shown in Figure 2, illustrating the steric crowding around

Inclusion of trans-resveratrol in methylated cyclodextrins: synthesis and solid-state structures

• Lee Trollope,
• Dyanne L. Cruickshank,
• Terence Noonan,
• Susan A. Bourne,
• Milena Sorrenti,
• Laura Catenacci and
• Mino R. Caira

Beilstein J. Org. Chem. 2014, 10, 3136–3151, doi:10.3762/bjoc.10.331

• -precipitation method and fully characterized by thermal and single crystal X-ray diffraction methods. For the complexes containing the fully methylated hosts TMA and TMB, thermal analysis revealed dehydration overlapping with fusion of the anhydrous complex, followed by final decomposition, whereas the DMB

First chemoenzymatic stereodivergent synthesis of both enantiomers of promethazine and ethopropazine

• Paweł Borowiecki,
• Daniel Paprocki and
• Maciej Dranka

Beilstein J. Org. Chem. 2014, 10, 3038–3055, doi:10.3762/bjoc.10.322

Aspergiloid I, an unprecedented spirolactone norditerpenoid from the plant-derived endophytic fungus Aspergillus sp. YXf3

• Zhi Kai Guo,
• Rong Wang,
• Wei Huang,
• Xiao Nian Li,
• Rong Jiang,
• Ren Xiang Tan and
• Hui Ming Ge

Beilstein J. Org. Chem. 2014, 10, 2677–2682, doi:10.3762/bjoc.10.282

• derived from Ginkgo biloba. Its structure was unambiguously established by analysis of HRMS–ESI and spectroscopic data, and the absolute configuration was determined by low-temperature (100 K) single crystal X-ray diffraction with Cu Kα radiation. This compound is structurally characterized by a new

• -temperature (100 K) single-crystal X-ray diffraction experiment, which is shown in Figure 3. As compound 1 has a relatively high percentage of oxygen, it shows enough anomalous dispersion of Cu Kα radiation and allows to determinate the absolute stereochemistry with the Hooft parameter 0.17(15) for 992

• Bijvoet pairs by single-crystal X-ray diffraction experiment [13]. Therefore, the absolute configurations of the chiral centers in 1 were established as 5R, 6S, 10R, 11R. This compound is structurally characterized by a new carbon skeleton with an unprecedented 6/5/6 tricyclic ring system bearing an α,β

One-pot four-component reaction for convenient synthesis of functionalized 1-benzamidospiro[indoline-3,4'-pyridines]

• Chao Wang,
• Yan-Hong Jiang and
• Chao-Guo Yan

Beilstein J. Org. Chem. 2014, 10, 2671–2676, doi:10.3762/bjoc.10.281

• indicate that this four-component reaction may have a widely variety of substrates. The structures of the prepared spiro[indoline-3,4’-pyridines] 1a–m were fully characterized with IR, 1H, 13C NMR, HRMS spectra and were further confirmed by single-crystal X-ray diffraction determination of the compound 1k

Formal total syntheses of classic natural product target molecules via palladium-catalyzed enantioselective alkylation

• Yiyang Liu,
• Marc Liniger,
• Ryan M. McFadden,
• Jenny L. Roizen,
• Jacquie Malette,
• Corey M. Reeves,
• Douglas C. Behenna,
• Masaki Seto,
• Jimin Kim,
• Justin T. Mohr,
• Scott C. Virgil and
• Brian M. Stoltz

Beilstein J. Org. Chem. 2014, 10, 2501–2512, doi:10.3762/bjoc.10.261

• ]. The relative stereochemistry of dysidiolide (29) was determined via single-crystal X-ray diffraction analysis, revealing a molecule with six stereocenters, two of which are quaternary carbons [45]. Several groups have reported total syntheses of this natural product [47][48][49][50][51][52][53], three

• –Danheiser chemistry [66][67]. E) Rhazinilam (−)-Rhazinilam (44) has been isolated from various plants including Rhazya strica decaisne [68], Melodinus australis [69], and Kopsia singapurensis [70]. Shortly after the first isolation, its structure was elucidated by single crystal X-ray diffraction analysis

Phosphinocyclodextrins as confining units for catalytic metal centres. Applications to carbon–carbon bond forming reactions

• Matthieu Jouffroy,
• Rafael Gramage-Doria,
• David Sémeril,
• Dominique Armspach,
• Dominique Matt,
• Werner Oberhauser and
• Loïc Toupet

Beilstein J. Org. Chem. 2014, 10, 2388–2405, doi:10.3762/bjoc.10.249

• coordinated water molecule appeared as a broad singlet at δ = 5.64 ppm in the 1H NMR spectrum recorded at −80 °C [45]. This chemical shift value is typical for aqua palladium complexes [49][50][51]. A single crystal X-ray diffraction study (Figure 2) confirmed the coordination of a {PdCl2(H2O)} fragment

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

• (6c) reacted much more slowly than 6a,b. The molecular structure of 7a·3CH3CN in the solid state was established by a single crystal X-ray diffraction analysis and is shown in Figure 1 (vide infra for a discussion of structural details). It is interesting to note that the chloride anion is trapped

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

• acenes can provide vital information about intermolecular interactions, single crystals of pentacenes 3a–d and 3g–j were grown and their solid-state arrangements determined by single crystal X-ray diffraction analysis (crystallographic details are provided in Supporting Information File 1). Pentacene 3a