Hoveyda–Grubbs catalysts with an N→Ru coordinate bond in a six-membered ring. Synthesis of stable, industrially scalable, highly efficient ruthenium metathesis catalysts and 2-vinylbenzylamine ligands as their precursors

• Kirill B. Polyanskii,
• Kseniia A. Alekseeva,
• Pavel V. Raspertov,
• Pavel A. Kumandin,
• Eugeniya V. Nikitina,
• Atash V. Gurbanov and
• Fedor I. Zubkov

Beilstein J. Org. Chem. 2019, 15, 769–779, doi:10.3762/bjoc.15.73

• were obtained as good crystals suitable for X-ray diffraction analysis. Unfortunately, we were not able to obtain single crystals of satisfactory quality for the morpholino-containing catalyst 11d. Still, the accessible X-ray structural information is sufficient to correlate structure with catalytic

Synthesis of 2H-furo[2,3-c]pyrazole ring systems through silver(I) ion-mediated ring-closure reaction

• Vaida Milišiūnaitė,
• Rūta Paulavičiūtė,
• Eglė Arbačiauskienė,
• Vytas Martynaitis,
• Wolfgang Holzer and
• Algirdas Šačkus

Beilstein J. Org. Chem. 2019, 15, 679–684, doi:10.3762/bjoc.15.62

• -catalyzed coupling of 4-iodo-1-phenyl-1H-pyrazol-3-ol with ethyne derivatives. The structures of the obtained target compounds were unequivocally confirmed by detailed 1H, 13C and 15N NMR spectroscopic experiments, HRMS and a single-crystal X-ray diffraction analyses. This silver(I)-mediated 5-endo-dig

• ) data and a single-crystal X-ray diffraction analysis. The 1H NMR spectra of compounds 4a–j revealed the characteristic H-3 proton singlet in the δ 7.60–7.77 ppm region as well as a H-4 proton singlet in the δ 6.06–6.74 ppm region. The 13C NMR spectra of 4a–j exhibited signals for the five carbon atoms

Catalyst-free assembly of giant tris(heteroaryl)methanes: synthesis of novel pharmacophoric triads and model sterically crowded tris(heteroaryl/aryl)methyl cation salts

• Rodrigo Abonia,
• Luisa F. Gutiérrez,
• Braulio Insuasty,
• Jairo Quiroga,
• Kenneth K. Laali,
• Chunqing Zhao,
• Gabriela L. Borosky,
• Samantha M. Horwitz and
• Scott D. Bunge

Beilstein J. Org. Chem. 2019, 15, 642–654, doi:10.3762/bjoc.15.60

• chemical shifts were referenced to TMS. GIAO magnetic shielding tensors were 31.88 for 1H, 182.5 for 13C, values related to the GIAO isotropic magnetic susceptibility. X-ray crystallography. Colorless crystals were isolated for 9{4,7,1} from acetonitrile and used for the following X-ray diffraction studies

Study on the regioselectivity of the N-ethylation reaction of N-benzyl-4-oxo-1,4-dihydroquinoline-3-carboxamide

• Pedro N. Batalha,
• Luana da S. M. Forezi,
• Maria Clara R. Freitas,
• Nathalia M. de C. Tolentino,
• Ednilsom Orestes,
• José Walkimar de M. Carneiro,
• Fernanda da C. S. Boechat and
• Maria Cecília B. V. de Souza

Beilstein J. Org. Chem. 2019, 15, 388–400, doi:10.3762/bjoc.15.35

• '/6' or C-3’/5’), 127.19 (C-4a), 126.72 (C-4’), 126.17 (C-5), 124.83 (C-6), 117.12 (C-8), 110.87 (C-3), 48.14 (NCH2CH3), 42.06 (CONHCH2), 14.33 (NCH2CH3). X-ray diffraction measurement Single crystal X-ray diffraction data of derivative 7 were collected on a Bruker D8 Venture diffractometer at room

• would also like to acknowledge the finantial support provided by Fundação Carlos Chagas Filho para o Amparo à Pesquisa do Estado do Rio de Janeiro (FAPERJ) and Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq). We are also grateful to the X-Ray Diffraction Multiuser Laboratory (http

Reusable and highly enantioselective water-soluble Ru(II)-Amm-Pheox catalyst for intramolecular cyclopropanation of diazo compounds

• Hamada S. A. Mandour,
• Yoko Nakagawa,
• Masaya Tone,
• Hayato Inoue,
• Nansalmaa Otog,
• Ikuhide Fujisawa,
• Soda Chanthamath and
• Seiji Iwasa

Beilstein J. Org. Chem. 2019, 15, 357–363, doi:10.3762/bjoc.15.31

• determined to be (1S,5R,6R) by single-crystal X-ray diffraction analysis (Supporting Information File 1) [51]. Since the stereoselectivity of products depends on the cis/trans geometry of the reactants, other stereoisomers such as the (1S,5R,6S) product was not formed in this catalytic cyclopropanation

Systematic synthetic study of four diastereomerically distinct limonene-1,2-diols and their corresponding cyclic carbonates

• Hiroshi Morikawa,
• Jun-ichi Yamaguchi,
• Shun-ichi Sugimura,
• Masato Minamoto,
• Yuuta Gorou,
• Hisatoyo Morinaga and
• Suguru Motokucho

Beilstein J. Org. Chem. 2019, 15, 130–136, doi:10.3762/bjoc.15.13

• those of LM5CCs by reference to the a and c signals in Figure 4. The coupling constants for the signal a support the structures shown in Figure 5. Indeed, the equatorial position of the isopropenyl group for 2c and 2d in the solid state was confirmed by X-ray diffraction analysis, as reported previously

Fabrication of supramolecular cyclodextrin–fullerene nonwovens by electrospinning

• Hiroaki Yoshida,
• Ken Kikuta and
• Toshiyuki Kida

Beilstein J. Org. Chem. 2019, 15, 89–95, doi:10.3762/bjoc.15.10

• , USA), X-ray diffraction (MiniFlex 300, Rigaku, Japan), and CLSM (FLUOVIEW FV1000, Olympus, Japan). The optimized electrospinning parameters were: (γ-CD–C60) voltage: 15 kV, distance between electrodes: 10 cm, flow rate: 3 mL/h; (β-CD–C60) voltage: 25 kV, distance between electrodes: 10 cm, flow rate

Synthesis, biophysical properties, and RNase H activity of 6’-difluoro[4.3.0]bicyclo-DNA

• Sibylle Frei,
• Adam K. Katolik and
• Christian J. Leumann

Beilstein J. Org. Chem. 2019, 15, 79–88, doi:10.3762/bjoc.15.9

• [43][44] followed by phosphitylation at the 3’-oxygen afforded the phosphoramidite 9. X-ray structure and molecular modeling of the 6’-diF-bc4,3 nucleoside To verify the relative configuration of nucleoside 6, crystals of this compound were subjected to X-ray diffraction analysis. The asymmetric unit

Mn-mediated sequential three-component domino Knoevenagel/cyclization/Michael addition/oxidative cyclization reaction towards annulated imidazo[1,2-a]pyridines

• Olga A. Storozhenko,
• Alexey A. Festa,
• Delphine R. Bella Ndoutoume,
• Alexander V. Aksenov,
• Alexey V. Varlamov and
• Leonid G. Voskressensky

Beilstein J. Org. Chem. 2018, 14, 3078–3087, doi:10.3762/bjoc.14.287

• single crystal X-ray diffraction study (Figure 2). The sequential domino reaction presumably starts with the Knoevenagel condensation of o-hydroxybenzaldehyde and N-(cyanomethyl)pyridinium salt forming styryl derivative A, which undergoes intramolecular cyclization to give 2-iminochromene salt 3

• NMR spectra and X-ray diffraction data. Acknowledgements The publication was prepared with the support of the “RUDN University Program 5-100” and RFBR Grant 18-33-00536. A.A.F and L.G.V express sincere gratitude to Prof. Lutz F. Tietze for an inspirational meeting in the University of Göttingen.

Nucleofugal behavior of a β-shielded α-cyanovinyl carbanion

• Rudolf Knorr and
• Barbara Schmidt

Beilstein J. Org. Chem. 2018, 14, 3018–3024, doi:10.3762/bjoc.14.281

• a nucleophile was not tried here but might serve to accumulate the organometallic equilibrium component for the purpose of spectroscopic characterization or X-ray diffraction analyses. (iv) Fission of the lithium alkoxide of the adduct 13 of adamantan-2-one appeared to be comparably fast on the

1,8-Bis(dimethylamino)naphthyl-2-ketimines: Inside vs outside protonation

• A. S. Antonov,
• A. F. Pozharskii,
• P. M. Tolstoy,
• A. Filarowski and
• O. V. Khoroshilova

Beilstein J. Org. Chem. 2018, 14, 2940–2948, doi:10.3762/bjoc.14.273

• 1867639-1867642). Acknowledgements This work was supported by the Russian Foundation for Basic Research (project 16-33-60030). Experimental measurements were performed in Centre for Magnetic Resonance, Chemical Analysis and Materials Research Centre, Centre for X-ray Diffraction Studies at St. Petersburg

Green synthesis of new chiral 1-(arylamino)imidazo[2,1-a]isoindole-2,5-diones from the corresponding α-amino acid arylhydrazides in aqueous medium

• Nadia Bouzayani,
• Jamil Kraїem,
• Sylvain Marque,
• Yakdhane Kacem,
• Abel Carlin-Sinclair,
• Jérôme Marrot and
• Béchir Ben Hassine

Beilstein J. Org. Chem. 2018, 14, 2923–2930, doi:10.3762/bjoc.14.271

• in a trans-orientation with H(4). In addition, various crystallization tests were carried out in order to confirm the absolute stereochemistry by X-ray diffraction. The chiral 3-(2-(methylthio)ethyl)-1-(phenylamino)-1H-imidazo[2,1-a]isoindole-2,5(3H,9bH)dione (5f) crystallized [44][45][46][47][48][49

Generation of 1,2-oxathiolium ions from (arysulfonyl)- and (arylsulfinyl)allenes in Brønsted acids. NMR and DFT study of these cations and their reactions

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

Beilstein J. Org. Chem. 2018, 14, 2897–2906, doi:10.3762/bjoc.14.268

• was supported by Russian Scientific Foundation (grant no. 18-13-00008). Spectral studies were performed at 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

Synthesis of mono-functionalized S-diazocines via intramolecular Baeyer–Mills reactions

• Miriam Schehr,
• Daniel Hugenbusch,
• Tobias Moje,
• Christian Näther and
• Rainer Herges

Beilstein J. Org. Chem. 2018, 14, 2799–2804, doi:10.3762/bjoc.14.257

• -functionalized S-diazocine 3 single crystals could be obtained, which were characterized by single crystal X-ray diffraction. The structure of 3 is the first crystal structure of a S-diazocine reported in the Cambridge Structural Database (CSD; version 5.39; Feb. 2018) [28]. This compound crystallizes in the

Molecular iodine-catalyzed one-pot multicomponent synthesis of 5-amino-4-(arylselanyl)-1H-pyrazoles

• Camila S. Pires,
• Daniela H. de Oliveira,
• Maria R. B. Pontel,
• Jean C. Kazmierczak,
• Roberta Cargnelutti,
• Diego Alves,
• Raquel G. Jacob and
• Ricardo F. Schumacher

Beilstein J. Org. Chem. 2018, 14, 2789–2798, doi:10.3762/bjoc.14.256

• copper salt. To confirm the structure of 6, its molecular structure was also analyzed by single-crystal X-ray diffraction (CCDC: 1853770). The molecular structure is demonstrated in Figure 1. Conclusion A variety of 4-(arylselanyl)-1H-pyrazol-5-amines was prepared in a one-pot multicomponent procedure

Unprecedented nucleophile-promoted 1,7-S or Se shift reactions under Pummerer reaction conditions of 4-alkenyl-3-sulfinylmethylpyrroles

• Takashi Go,
• Akane Morimatsu,
• Hiroaki Wasada,
• Genzoh Tanabe,
• Osamu Muraoka,
• Yoshiharu Sawada and
• Mitsuhiro Yoshimatsu

Beilstein J. Org. Chem. 2018, 14, 2722–2729, doi:10.3762/bjoc.14.250

• determined by analysing the single-crystal X-ray diffraction spectrum of the corresponding sulfone of 4a; the structure was a pyrrole bearing both 3-sulfanylmethyl and 4-allylaminomethyl groups (see Supporting Information File 1). To develop a useful Pummerer reaction procedure, we selected allylamine

• low. These products were confirmed by X-ray spectra and/or single-crystal X-ray diffraction patterns. The unique S-shift reactions in the formation of either pyrrolo[3,2-c]azepines or diols proceeded according to the mechanism we proposed, which is depicted in Scheme 4. Sulfoxide 13 is activated by

Transition metal-free oxidative and deoxygenative C–H/C–Li cross-couplings of 2H-imidazole 1-oxides with carboranyl lithium as an efficient synthetic approach to azaheterocyclic carboranes

• Lidia A. Smyshliaeva,
• Mikhail V. Varaksin,
• Pavel A. Slepukhin,
• Oleg N. Chupakhin and
• Valery N. Charushin

Beilstein J. Org. Chem. 2018, 14, 2618–2626, doi:10.3762/bjoc.14.240

• Information Supporting Information File 444: Experimental procedures, characterization data, copies of the 1H, 13C, 11B NMR spectra and X-ray diffraction studies. Acknowledgements This study was supported by the Russian Ministry of Education and Science (State contract 4.6351.2017/8.9) and the Russian

Efficient catalytic alkyne metathesis with a fluoroalkoxy-supported ditungsten(III) complex

• Henrike Ehrhorn,
• Janin Schlösser,
• Dirk Bockfeld and
• Matthias Tamm

Beilstein J. Org. Chem. 2018, 14, 2425–2434, doi:10.3762/bjoc.14.220

• formation of the complex [W2{OC(CF3)Me2}6(NHMe2)] (W2F3·NHMe2) (Scheme 2). The additional amine ligand stems from the protonolysis reaction of the amide with the fluorinated alcohol. Brown crystals suitable for X-ray diffraction analysis were isolated from a saturated pentane solution at −40 °C. The

• molecular structure of this complex was established by X-ray diffraction analysis. The ORTEP diagram is shown in Figure 2, and selected bond lengths and angles are displayed in Table 1. The tungsten–tungsten triple bond of 2.3452(2) Å falls in the range of previously reported bond lengths of this type [69

• from [NaW2Cl7(THF)5] [86]. The 13C and 19F NMR spectra are also consistent with literature values. Crystals of W2F3 suitable for X-ray diffraction analysis were obtained upon cooling a saturated pentane solution to −40 °C. Unfortunately, the crystal structure suffers from severe disorder. Each tungsten

Bioinspired cobalt cubanes with tunable redox potentials for photocatalytic water oxidation and CO₂ reduction

• Zhishan Luo,
• Yidong Hou,
• Jinshui Zhang,
• Sibo Wang and
• Xinchen Wang

Beilstein J. Org. Chem. 2018, 14, 2331–2339, doi:10.3762/bjoc.14.208

• TECNAIG2F20 instrument. Powder X-ray diffraction (XRD) patterns were collected on Bruker D8 Advance diffractometer with Cu K1 radiation (λ = 1.5406 Å). Photocatalytic test for water oxidation system [69]: Photocatalytic O2 production was carried out in a Pyrex top-irradiation reaction vessel connected to a

Determining the predominant tautomeric structure of iodine-based group-transfer reagents by ¹⁷O NMR spectroscopy

• Nico Santschi,
• Cody Ross Pitts,
• Benson J. Jelier and
• René Verel

Beilstein J. Org. Chem. 2018, 14, 2289–2294, doi:10.3762/bjoc.14.203

• corroboration came about by successfully encapsulating 5b, an oil under ambient conditions, in a metal-organic framework (5b@MOF). This non-trivial protocol rendered it amenable to X-ray diffraction studies confirming the aforementioned structural reassignment. From a theoretical standpoint, acyclic isomer 5b

Novel photochemical reactions of carbocyclic diazodiketones without elimination of nitrogen – a suitable way to N-hydrazonation of C–H-bonds

• Liudmila L. Rodina,
• Xenia V. Azarova,
• Jury J. Medvedev,
• Dmitrij V. Semenok and
• Valerij A. Nikolaev

Beilstein J. Org. Chem. 2018, 14, 2250–2258, doi:10.3762/bjoc.14.200

• electrospray ionization (ESI-QTOF). Chemical shifts are reported in ppm, and coupling constants are given in hertz (Hz). All signals in NMR spectra were normalized relative to signals of CНCl3 (δ = 7.26 ppm in 1H NMR) and CDCl3 (δ = 77.0 in 13C NMR spectra). For single crystal X-ray diffraction experiments of

• compounds 1c (CCDC 1584937) and 2b (CCDC 1584938). Acknowledgements The authors express their gratitude to the SPbSU resource centers: "Center for Magnetic Resonance", "Chemical Analysis and Materials Research Centre" and "Resource Education Center" and "Research Centre for X-Ray Diffraction Methods of

Synthesis and post-functionalization of alternate-linked-meta-para-[2ⁿ.1ⁿ]thiacyclophanes

• Wout De Leger,
• Koen Adriaensen,
• Koen Robeyns,
• Luc Van Meervelt,
• Joice Thomas,
• Björn Meijers,
• Mario Smet and
• Wim Dehaen

Beilstein J. Org. Chem. 2018, 14, 2190–2197, doi:10.3762/bjoc.14.192

• was further analysed by X-ray diffraction. Results and Discussion Macrocyclization Macrocyclization and post-functionalization of cyclophanes is of high interest for the development of various applications in molecular recognition. Based on our previous one-pot procedure towards homothiacalixarenes

• yield of 91%. The 3D structure of macrocycle 6 was confirmed by single crystal X-ray diffraction and shows approximate twofold rotational symmetry (point group C2, Figure 1). The dihedral angles between the aromatic rings are given in Table S2 (Supporting Information File 1, ring numbering as shown in

Evaluation of dispersion type metal···π arene interaction in arylbismuth compounds – an experimental and theoretical study

• Ana-Maria Preda,
• Małgorzata Krasowska,
• Lydia Wrobel,
• Philipp Kitschke,
• Phil C. Andrews,
• Jonathan G. MacLellan,
• Lutz Mertens,
• Marcus Korb,
• Tobias Rüffer,
• Heinrich Lang,
• Alexander A. Auer and
• Michael Mehring

Beilstein J. Org. Chem. 2018, 14, 2125–2145, doi:10.3762/bjoc.14.187

• the analysis of single crystal X-ray diffraction data and computational studies. First, the crystal structures of polymorphs of Ph3Bi (1) are described emphasizing on the description of London dispersion type bismuth···π arene interactions and other van der Waals interactions in the solid state and

• rarely a more compact morphology. Both types of crystals of 2 were suitable for single crystal X-ray diffraction analysis and revealed the formation of two polymorphs 2a (colorless acicular crystals) and 2b (light yellow block-shaped crystals) in the solid state. Polymorph 2a crystallizes in the

Synthesis of new p-tert-butylcalix[4]arene-based polyammonium triazolyl amphiphiles and their binding with nucleoside phosphates

• Vladimir A. Burilov,
• Guzaliya A. Fatikhova,
• Mariya N. Dokuchaeva,
• Ramil I. Nugmanov,
• Diana A. Mironova,
• Pavel V. Dorovatovskii,
• Victor N. Khrustalev,
• Svetlana E. Solovieva and
• Igor S. Antipin

Beilstein J. Org. Chem. 2018, 14, 1980–1993, doi:10.3762/bjoc.14.173

• = 100 K: a = 15.003(3) Å, b = 19.652(4) Å, c = 15.368(3) Å, β = 104.71(3)°, V = 4382.6(16) Å3, Z = 4, dcalcd = 1.232 g/cm3, F(000) = 1728, μ = 0.172 mm−1. X-ray diffraction data were collected at the ‘Belok’ beamline (λ = 0.96990 Å) of the National Research Center ‘Kurchatov Institute’ (Moscow, Russian

A hemicryptophane with a triple-stranded helical structure

• Augustin Long,
• Olivier Perraud,
• Erwann Jeanneau,
• Christophe Aronica,
• Jean-Pierre Dutasta and
• Alexandre Martinez

Beilstein J. Org. Chem. 2018, 14, 1885–1889, doi:10.3762/bjoc.14.162

• of a solution of cage 1 in a 1:1 mixture of CHCl3/MeOH affords crystals suitable for X-ray diffraction. In the solid, the hemicryptophane cage presents a perfect C3 symmetry (Figure 2). Further examination of the crystal structure reveals that 1 adopts a chiral conformation where the three linkers