Synthesis of tetrasubstituted pyrazoles containing pyridinyl substituents

• Josef Jansa,
• Ramona Schmidt,
• Ashenafi Damtew Mamuye,
• Laura Castoldi,
• Alexander Roller,
• Vittorio Pace and
• Wolfgang Holzer

Beilstein J. Org. Chem. 2017, 13, 895–902, doi:10.3762/bjoc.13.90

• (pyridin-2-yl)-substituted derivatives 3a,b upon treatment with 1.1 equivalents of n-BuLi at −78 °C. Subsequent reaction with CO2 led to almost complete conversion to 4a,b as detected by TLC (Scheme 3). In contrast, with 3,5-di(pyridin-3-yl)-substituted derivatives 3c,d, the lithiation reaction was slower

• and not fully complete, also the subsequent reaction with CO2 was more sluggish in comparison to 3a,b what resulted in lower yields. The increased reactivity of 3a,b compared to 3c,d may be explained by the ability of the former to stabilize the intermediate organolithium species by chelation due to

The effect of cyclodextrin complexation on the solubility and photostability of nerolidol as pure compound and as main constituent of cabreuva essential oil

• Joyce Azzi,
• Pierre-Edouard Danjou,
• David Landy,
• Steven Ruellan,
• Lizette Auezova,
• Hélène Greige-Gerges and
• Sophie Fourmentin

Beilstein J. Org. Chem. 2017, 13, 835–844, doi:10.3762/bjoc.13.84

• investigated by TOC analysis using a Shimadzu TOC-VCSH analyzer. It is based on the production of carbon dioxide (CO2) following oxidation of organic compounds. CO2 is then detected using a high-sensitivity infrared gas analyzer (NDIR). First, TOC was measured for the CD solution (TOCCD). Then, the amount of

Continuous-flow processes for the catalytic partial hydrogenation reaction of alkynes

• Carmen Moreno-Marrodan,
• Francesca Liguori and
• Pierluigi Barbaro

Beilstein J. Org. Chem. 2017, 13, 734–754, doi:10.3762/bjoc.13.73

• −1, Table 1, entries 29, 30) [137]. Lower performances were observed using packed-bed catalysts and conventional support materials [123], an amorphous Pd81Si19 alloy catalyst in supercritical CO2 (76% sel. at 91% conversion, 358 K) [149] or a capillary reactor (i.d. 250 μm) internally coated with Pd

Pd- and Cu-catalyzed approaches in the syntheses of new cholane aminoanthraquinone pincer-like ligands

• Nikolay V. Lukashev,
• Gennadii A. Grabovyi,
• Dmitry A. Erzunov,
• Alexey V. Kazantsev,
• Gennadij V. Latyshev,
• Alexei D. Averin and
• Irina P. Beletskaya.

Beilstein J. Org. Chem. 2017, 13, 564–570, doi:10.3762/bjoc.13.55

• +, Fe2+, Co2+, Ni2+, Zn2+, Cu2+, Ag+, Pb2+, Hg2+, Cr3+, Ga3+, Y3+, In3+) on the UV spectrum of 5c (Figure 2). The qualitative selectivity test by stepwise addition of 1, 2, 3, and 5 equiv of metal perchlorates in MeCN to the solution of 5c in MeCN revealed that the majority of cations did not influence

Decarboxylative and dehydrative coupling of dienoic acids and pentadienyl alcohols to form 1,3,6,8-tetraenes

• Ghina’a I. Abu Deiab,
• Mohammed H. Al-Huniti,
• I. F. Dempsey Hyatt,
• Emma E. Nagy,
• Kristen E. Gettys,
• Sommayah S. Sayed,
• Christine M. Joliat,
• Paige E. Daniel,
• Rupa M. Vummalaneni,
• Andrew T. Morehead Jr,
• Andrew L. Sargent and
• Mitchell P. Croatt

Beilstein J. Org. Chem. 2017, 13, 384–392, doi:10.3762/bjoc.13.41

• materials [10][11][12][13][14][15][16][17][18]. Another approach to the formation of C–C bonds is through decarboxylative coupling reactions (Scheme 1). This can be arrived in a one-component fashion via the removal of CO2 from an ester or in a two-component manner by removal of CO2 from a carboxylic acid

Continuous N-alkylation reactions of amino alcohols using γ-Al₂O₃ and supercritical CO₂: unexpected formation of cyclic ureas and urethanes by reaction with CO₂

• Emilia S. Streng,
• Darren S. Lee,
• Michael W. George and
• Martyn Poliakoff

Beilstein J. Org. Chem. 2017, 13, 329–337, doi:10.3762/bjoc.13.36

• -optimising reactor, resulting in moderate to high yields of the target products. Carrying out the reaction in scCO2 was shown to be beneficial, as higher yields were obtained in the presence of CO2 than in its absence. A surprising discovery is that, in addition to cyclic amines, cyclic ureas and urethanes

• could be synthesised by incorporation of CO2 from the supercritical solvent into the product. Keywords: continuous flow; heterocycle; N-alkylation; self-optimisation; supercritical CO2; Introduction N-alkylated amines are an important motif present in a range of pharmaceutically and industrially

• gases that are beyond the critical point (e.g., the critical point for CO2 is 31.1 °C and 73.9 bar); in this phase the gas exhibits unique properties and behaves both like a liquid and gas. Using inert supercritical gases as reaction solvents is a greener alternative to using conventional flammable or

NMR reaction monitoring in flow synthesis

• M. Victoria Gomez and
• Antonio de la Hoz

Beilstein J. Org. Chem. 2017, 13, 285–300, doi:10.3762/bjoc.13.31

• second flow reactor the Grignard was reacted with CO2 to obtain carboxylic acids (Figure 5). The whole process was monitored by on-line 1H NMR spectroscopy using a low field NMR instrument (Spinsolve-60 from Magritek). The reaction was analysed by in-line NMR and off-line with a standard NMR tube. In the

Spectral and DFT studies of anion bound organic receptors: Time dependent studies and logic gate applications

• Srikala Pangannaya,
• Neethu Padinchare Purayil,
• Shweta Dabhi,
• Venu Mankad,
• Prafulla K. Jha,
• Satyam Shinde and
• Darshak R. Trivedi

Beilstein J. Org. Chem. 2017, 13, 222–238, doi:10.3762/bjoc.13.25

• receptors R1 and R2 (4.5 × 10−5 M in DMSO) towards the cations Na+, K+, Ca2+, Mg2+, Al3+, Co2+, Ni2+, Cu2+, Zn2+, Pb2+, Cd2+ and Hg2+ that were used as nitrate salts at a concentration of 10−3 M in distilled water. A strong colorimetric response of receptor R1 towards Hg2+ cations resulting in a color

A postsynthetically 2’-“clickable” uridine with arabino configuration and its application for fluorescent labeling and imaging of DNA

• Heidi-Kristin Walter,
• Bettina Olshausen,
• Ute Schepers and
• Hans-Achim Wagenknecht

Beilstein J. Org. Chem. 2017, 13, 127–137, doi:10.3762/bjoc.13.16

• described in Supporting Information File 1. Cell experiments and confocal fluorescence microsopy. Human cervix carcinoma cells (HeLa cells) were cultured in Dulbecco’s modified Eagle medium (DMEM) supplemented with 10% fetal calf serum and 1% penicillin/streptomycin at 37 °C in a 5% CO2 atmosphere. 24 h

• to the cells. The cells were incubated for 24 h with the respective transfection mixture at 37 °C in a 5% CO2 atmosphere. The visualization of the DNA duplexes was performed by confocal laser scanning microscopy using a Leica TCS SPE (DMi8) inverted microscope with an ACS APO 63×/1.30 oil objective

Synthesis and evaluation of anti-oxidant and cytotoxic activities of novel 10-undecenoic acid methyl ester based lipoconjugates of phenolic acids

• Naganna Narra,
• Shiva Shanker Kaki,
• Rachapudi Badari Narayana Prasad,
• Sunil Misra,
• Koude Dhevendar,
• Venkateshwarlu Kontham and
• Padmaja V. Korlipara

Beilstein J. Org. Chem. 2017, 13, 26–32, doi:10.3762/bjoc.13.4

• maintained in DMEM supplemented with 10% FBS, 2 mM L-glutamine, 100 U/mL penicillin, and 100 μg/mL streptomycin at 37 °C in a 5% CO2 incubator. After seeding of cells in 96 well culture plates, they were allowed to attach properly. Test compounds of different concentrations ranging from 1 to 50 µM were added

Synthesis of multi-lactose-appended β-cyclodextrin and its cholesterol-lowering effects in Niemann–Pick type C disease-like HepG2 cells

• Keiichi Motoyama,
• Rena Nishiyama,
• Yuki Maeda,
• Taishi Higashi,
• Yoichi Ishitsuka,
• Yuki Kondo,
• Tetsumi Irie,
• Takumi Era and
• Hidetoshi Arima

Beilstein J. Org. Chem. 2017, 13, 10–18, doi:10.3762/bjoc.13.2

• Medium (DMEM, Nissui Pharmaceuticals, Tokyo, Japan), containing penicillin (1 × 105 mU/mL), streptomycin (0.1 mg/mL) and supplemented with 10% fetal bovine serum (FBS), in a humidified incubator with 5% CO2. NPC-like HepG2 cells accumulated with high amounts of cholesterol were obtained after 48 h

Supramolecular frameworks based on [60]fullerene hexakisadducts

• Andreas Kraft,
• Johannes Stangl,
• Ana-Maria Krause,
• Klaus Müller-Buschbaum and
• Florian Beuerle

Beilstein J. Org. Chem. 2017, 13, 1–9, doi:10.3762/bjoc.13.1

• , C(CH3)3), 141.15 (24C, C60 sp2), 145.99 (24C, C60 sp2), 163.75 (12C, O2CCH2CO2), 171.89 ppm (12C, CO2 t-Bu); UV–vis (CH2Cl2) λ: 281, 315 (sh), 334 (sh) nm; MS (MALDI, DCTB, pos) m/z: 3038 [M]+; anal, calcd for C174H180O48: C, 68.76; H, 5.97; found: C, 68.87; H, 6.09. Hexakisadduct C4: TFA (1.7 mL

Versatile synthesis of end-reactive polyrotaxanes applicable to fabrication of supramolecular biomaterials

• Atsushi Tamura,
• Asato Tonegawa,
• Yoshinori Arisaka and
• Nobuhiko Yui

Beilstein J. Org. Chem. 2016, 12, 2883–2892, doi:10.3762/bjoc.12.287

• medium (DMEM) (Wako Pure Chemical Industries) containing 10% fetal bovine serum (FBS) (Sigma-Aldrich), 100 units/mL penicillin, and 100 µg/mL streptomycin (Wako Pure Chemical Industries) in a humidified 5% CO2 atmosphere at 37 °C. HeLa cells were plated on 35 mm glass-bottom dishes (Iwaki, Tokyo, Japan

Green chemistry

• Luigi Vaccaro

Beilstein J. Org. Chem. 2016, 12, 2763–2765, doi:10.3762/bjoc.12.273

• recovery and reuse of the materials needed for a synthetic process. It is also very important to promote the use of biomass-derived chemicals that feature an intrinsically lower CO2 consumption. Additionally, the pivotal role of catalysis is indisputable. Significant efforts are being directed towards the

Et₃B-mediated and palladium-catalyzed direct allylation of β-dicarbonyl compounds with Morita–Baylis–Hillman alcohols

• Ahlem Abidi,
• Yosra Oueslati and
• Farhat Rezgui

Beilstein J. Org. Chem. 2016, 12, 2402–2409, doi:10.3762/bjoc.12.234

• ], and palladium (0, II) [9][10] as the catalyst or by converting the allylic alcohols into esters of inorganic acids, e.g., As2O3 [11], B2O3 [12], CO2 [13][14]. More recently the Lewis acids, such as, Ti(OiPr )4 [15], BEt3 [16][17][18][19], BPh3 [20], SnCl2 [21], and FeCl3 [22], have also been reported

Robust C–C bonded porous networks with chemically designed functionalities for improved CO₂ capture from flue gas

• Damien Thirion,
• Joo S. Lee,
• Ercan Özdemir and
• Cafer T. Yavuz

Beilstein J. Org. Chem. 2016, 12, 2274–2279, doi:10.3762/bjoc.12.220

• Technology (KAIST), Guseong Dong, Yuseong Gu, Daejeon 305–701, Korea 10.3762/bjoc.12.220 Abstract Effective carbon dioxide (CO2) capture requires solid, porous sorbents with chemically and thermally stable frameworks. Herein, we report two new carbon–carbon bonded porous networks that were synthesized

• COP-156-amine showed fast and increased CO2 uptake under simulated moist flue gas conditions compared to the starting network and usual industrial CO2 solvents, reaching up to 7.8 wt % uptake at 40 °C. Keywords: C–C bond; CO2 capture; microporous materials; porous polymers; postmodification

• hydroxylamine converted into amidoxime groups (COP-156-amidoxime). The COP-156-amine proved increased affinity towards CO2 with stronger binding energy, especially under moist conditions, reaching up to 7.8 wt % at 40 °C, a 2.1 wt % increase when compared to the original COP-156. Despite the promise

Isosorbide and dimethyl carbonate: a green match

• Fabio Aricò and
• Pietro Tundo

Beilstein J. Org. Chem. 2016, 12, 2256–2266, doi:10.3762/bjoc.12.218

• mixture (entry 1, Table 3). However, repeating the reaction under anhydrous conditions, the selectivity towards DCI increased to 85% (entry 2, Table 3). Most probably, even a small amount of water can affect the outcome of the reaction as it can hydrolyse the DMC molecule into CO2 and methanol. The latter

Tunable microwave-assisted method for the solvent-free and catalyst-free peracetylation of natural products

• Manuela Oliverio,
• Paola Costanzo,
• Monica Nardi,
• Carla Calandruccio,
• Raffaele Salerno and
• Antonio Procopio

Beilstein J. Org. Chem. 2016, 12, 2222–2233, doi:10.3762/bjoc.12.214

• (3.8 mL, 10 mmol NaHCO3) was added. After the evolution of CO2, the precipitation of the peracetylated product was observed. The products were separated by simple decantation. For compounds which do not precipitate upon addition of NaHCO3, an extraction with AcOEt was needed. The organic phase, after

Varioloid A, a new indolyl-6,10b-dihydro-5aH-[1]benzofuro[2,3-b]indole derivative from the marine alga-derived endophytic fungus Paecilomyces variotii EN-291

• Peng Zhang,
• Xiao-Ming Li,
• Xin-Xin Mao,
• Attila Mándi,
• Tibor Kurtán and
• Bin-Gui Wang

Beilstein J. Org. Chem. 2016, 12, 2012–2018, doi:10.3762/bjoc.12.188

• previously reported methods [24][25]. Briefly, the cells cited above were grown in RPMI 1640 (Sigma R6504) medium supplemented with 10% fetal calf serum (Gibco 16000-044) at 37 °C in humidified air with 5% CO2. Then the cell lines were treated with test compounds for 48 h, and subsequently MTT solution was

Hydroxy-functionalized hyper-cross-linked ultra-microporous organic polymers for selective CO₂ capture at room temperature

• Partha Samanta,
• Priyanshu Chandra and
• Sujit K. Ghosh

Beilstein J. Org. Chem. 2016, 12, 1981–1986, doi:10.3762/bjoc.12.185

• , H2 and O2 at room temperature. A high isosteric heat of adsorption (Qst) has been obtained for both materials because of strong interactions between polar –OH groups and CO2 molecules. Keywords: carbon dioxide capture; hyper-cross-linked polymer; metal-organic framework; microporous organic polymer

• , loss of plankton due to warming seas. There are many heat-trapping greenhouse gases present in the atmosphere (from methane to water vapour), but CO2 puts us at the greatest risk if it continues to accumulate in the atmosphere. This is due to the fact that CO2 remains in the atmosphere in a time scale

• of hundred years in contrast to other greenhouse gases which leave the atmosphere with relatively smaller time scale [1]. The CO2 long life in the atmosphere provides the clearest possible rationale for carbon dioxide capture and storage. Previously, different types of amine solvents were employed to

Ionic liquids as transesterification catalysts: applications for the synthesis of linear and cyclic organic carbonates

• Maurizio Selva,
• Alvise Perosa,
• Sandro Guidi and
• Lisa Cattelan

Beilstein J. Org. Chem. 2016, 12, 1911–1924, doi:10.3762/bjoc.12.181

• , P; n = 4, 6, 8, Ph), obtained by the methylation of trialkylphosphines or -amines with nontoxic DMC (Scheme 3, top) [34][35]. Such methyl carbonate onium salts are versatile platforms as they allow access to a number of ionic liquids via anion-metathesis reactions, which produce only CH3OH and CO2

• feedstocks, in particular to CO, except that its thermodynamic stability poses severe challenges. This potential limitation was overcome by the Asahi Kasei Corp. that recently industrialized a catalytic polycarbonate production process based on the use of carbon dioxide (CO2) for the synthesis of DMC as an

• intermediate towards the diphenyl carbonate monomer. The first step is the insertion of CO2 into ethylene oxide to give ethylene carbonate, which is catalyzed by onium salts. The second step involves the transesterification of ethylene carbonate with methanol. The reaction is carried out in a continuous

Cross-linked cyclodextrin-based material for treatment of metals and organic substances present in industrial discharge waters

• Élise Euvrard,
• Nadia Morin-Crini,
• Coline Druart,
• Justine Bugnet,
• Bernard Martel,
• Cesare Cosentino,
• Virginie Moutarlier and
• Grégorio Crini

Beilstein J. Org. Chem. 2016, 12, 1826–1838, doi:10.3762/bjoc.12.172

• hydrocarbons (PAH) and three alkylphenols (AP), the material exhibited high adsorption capacities: >99% of Co2+, Ni2+ and Zn2+ were removed, between 65 and 82% of the PAHs, as well as 69 to 90% of the APs. Due to the structure of the polymer and its specific characteristics, such as the presence of carboxylic

• +, Co2+, Cr3+, Ni2+ and Zn2+, respectively. Moreover, it appears that a polymer concentration of 2 g·L−1 is enough to treat an inorganic load of 50 mg·L−1. Thus, for all the following experiments, the polymers were activated and a concentration of 2 g·L−1 was used. Adsorption kinetics Figure 6 shows the

• the metals. At 1 mg·L−1 the adsorption kinetics was fast: in 5 min equilibrium was reached for the metals except for Al3+ (240 min). At 10 mg·L−1 for Co2+, Ni2+ and Zn2+, equilibrium time increased to 30 min, while for Al3+ and Cr3+ it decreased to 30 min. These results were obtained in triplicate

A flow reactor setup for photochemistry of biphasic gas/liquid reactions

• Josef Schachtner,
• Patrick Bayer and
• Axel Jacobi von Wangelin

Beilstein J. Org. Chem. 2016, 12, 1798–1811, doi:10.3762/bjoc.12.170

• , O3, H2, Cl2, acetylene, NOx, CO, CO2, etc.) but obviously bear several challenges with regard to a reproducible and precise control of the addition and mixing of the three phases: the liquid phase, containing organic substrates, the photo-active component (catalyst or sensitizer), the solvent, and

Amidofluorene-appended lower rim 1,3-diconjugate of calix[4]arene: synthesis, characterization and highly selective sensor for Cu²⁺

• Rahman Hosseinzadeh,
• Mohammad Nemati,
• Reza Zadmard and
• Maryam Mohadjerani

Beilstein J. Org. Chem. 2016, 12, 1749–1757, doi:10.3762/bjoc.12.163

• by adding 10 equivalents of different metal ions as perchlorate salts (Cu2+, Hg2+, Pb2+, Zn2+,Co2+, Ni2+, Cd2+, Ag+, Ba2+, K+, Na+ and Li+). Unlike Cu2+ ions, the addition of 10 equiv of other metal ions to the 1.0 × 10−5 M solutions of L resulted in no significant changes in the absorption spectra

• +, Co2+, Ni2+, Cd2+, Ag+, Ba2+, K+, Na+ and Li+. The fluorescence spectra showed almost no obvious change relative to the free ligand L (Figure 4). Titration of L with Cu2+ resulted in a gradual quenching of the fluorescence emission at the 365 nm band as a function of increasing Cu2+ concentration. The

Rearrangements of organic peroxides and related processes

• Ivan A. Yaremenko,
• Vera A. Vil’,
• Dmitry V. Demchuk and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2016, 12, 1647–1748, doi:10.3762/bjoc.12.162