bluuebunny/crossref_metadata_2025 huggingface dataset:
Anhydrous proton‐conducting electrolyte based on a nematic poly(methyl acrylate) containing sulfonated side chains
Authors: Liang Ting , Wu Yong , Tan Shuai , Wang Caihong
Published: January 2014

A nematic poly(methyl acrylate) containing terminal sulfonic acids in side chains was prepared by etherification of a brominated mesomorphic precursor with 2‐hydroxyethanesulfonic acid sodium salt. Differential scanning calorimetry measurements and polarized light microscopy observation revealed that the sulfonated polymer exhibited the nematic mesophase at medium temperatures (189–227°C). Electrochemical impedance spectroscopy measurements showed that temperature dependence of anhydrous proton conductivity for the nematic polymer followed the Arrhenius law and that the estimated activation energy was 95 kJ mol−1 in the nematic phase. The proton conductivities of the nematic polymer were two orders of magnitude higher than those of anhydrous Nafion®117 membrane at the same temperature. The enhanced anhydrous proton conductivities of the polymeric electrolyte were ascribed to the orientational order and fluidity of the nematic liquid crystal. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40382.
Processing and thermal properties of composites based on recycled PET, sisal fibers, and renewable plasticizers
Authors: de Oliveira Santos Rachel Passos , Castro Daniele Oliveira , Ruvolo‐Filho Adhemar Collà , Frollini Elisabete
Published: January 2014

This investigation focuses on the preparation of bio‐based composites from recycled poly (ethylene terephthalate) (PET) and sisal fibers (3 cm, 15 wt %), via thermopressing process. Plasticizers derived from renewable raw materials are used, namely, glycerol, tributyl citrate (TBC) and castor oil (CO), to decrease the melting point of the recycled PET (Tm ∼ 265°C), which is sufficiently high to initiate the thermal decomposition of the lignocellulosic fiber. All used materials are characterized by thermogravimetric analysis and differential scanning calorimetry, and the composites are also characterized via dynamic mechanical thermal analysis. The storage modulus (30°C) and the tan δ peak values of CT [PET/sisal/TBC] indicate that TBC also acts as a compatibilizing agent at the interface fiber/PET, as well as a plasticizer. To compare different processing methods, rheometry/thermopressing and compression molding are used to prepare the recycled PET/sisal/glycerol/CO composites. These two different methods of processing show no significant influence on the thermal properties of these composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40386.
Modification of jute fabric via laccase/t‐BHP‐mediated graft polymerization with acrylamide
Authors: Dong Aixue , Yuan Jiugang , Wang Qiang , Fan Xuerong
Published: January 2014

Enzymatic processes provide new perspectives for the modification of lignocellulose materials. Lignin is an excellent substrate for laccase, and the modification of lignin‐rich jute fabric via graft polymerization with acrylamide (AAm) mediated by laccase and tert‐butyl hydroperoxide (t‐BHP) was investigated in this study. The products obtained were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The grafting rate was determined in terms of elemental analysis. The hydrophilicity and thermal and dyeing properties of the modified jute fabric were studied. The results supported the conclusion that the polyacrylamide was grafted on the lignin of the jute fiber by laccase in coordination with t‐BHP, representing a grafting rate of 2.87%. The hydrophilicity, thermostability, dye uptake, and dyeing depth of the jute fiber were increased after the enzymatic graft modification with AAm. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40387.
Properties and weldability of plasticized polylactic acid films
Authors: Stoehr Neda , Baudrit Benjamin , Haberstroh Edmund , Nase Michael , Heidemeyer Peter , Bastian Martin
Published: January 2014

The objectives of the presented work were to investigate films based on polylactic acid (PLA) and polyethylene glycol (PEG) in order to improve ductility and weldability of PLA films. The effect of plasticizer amount on the thermal, rheological, and mechanical properties of PLA plasticized films was investigated. The PEG content does affect the glass transition and the cold crystallization temperature of PLA in blends, while the melting temperature was not affected by the addition of PEG. The complex viscosity of the neat PLA granules and of plasticized films showed strong temperature and angular velocity dependence. The Young's modulus and tensile strength of plasticized films were improved with increasing plasticizer concentration, while the elongation at break stays rather constant. Plasticized PLA films were furthermore heat welded. These investigations showed that plasticized PLA films can be welded by heat welding. The obtained weld strength is strongly depending on the PEG amount as well as on selected welding parameters. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40394.
Analysis of normal and modified nucleosides in urine samples by high‐performance liquid chromatography with different stationary phases
Authors: Studzińska S , Buszewski Bogusław
Published: January 2014

The main aim of the present work was to study the retention behavior and quantification of nine nucleosides with the use of octadecyl, alkylamide, cholesterol and alkyl‐phosphate stationary phases. The influence of organic solvent and buffer concentration on the separation of these compounds was under investigation. The retention factor had the highest values for the octadecyl and cholesterol packing materials. Complete separation of all the studied nucleosides was achieved in case of cholesterol stationary phase. The optimized separation method was applied for the quantification of nucleosides in the urine samples. Calibration plots showed good linearity (R2 > 0.999) and the limits of detection were in a range of 0.3–0.5 µg/mL, while the limits of quantitation were >0.9 µg/mL. Accuracy was in the range of 5–11%. Copyright © 2014 John Wiley & Sons, Ltd.
The attentional‐relevance and temporal dynamics of visual‐tactile crossmodal interactions differentially influence early stages of somatosensory processing
Authors: Popovich Christina , Staines W. Richard
Published: January 2014

Background

Crossmodal interactions between relevant visual and tactile inputs can enhance attentional modulation at early stages in somatosensory cortices to achieve goal‐oriented behaviors. However, the specific contribution of each sensory system during attentional processing remains unclear. We used EEG to investigate the effects of visual priming and attentional relevance in modulating somatosensory cortical responses.

Methods

Healthy adults performed a sensory integration task that required scaled motor responses dependent on the amplitudes of tactile and visual stimuli. Participants completed an attentional paradigm comprised of 5 conditions that presented sequential or concurrent pairs of discrete stimuli with random amplitude variations: 1) tactile‐tactile (TT), 2) visual‐visual (VV), 3) visual‐tactile simultaneous (SIM), 4) tactile‐visual delay (TVd), and 5) visual‐tactile delay (VTd), each with a 100 ms temporal delay between stimulus onsets. Attention was directed to crossmodal conditions and graded motor responses representing the summation of the 2 stimulus amplitudes were made.

Results

Results of somatosensory ERPs showed that the modality‐specific components (P50, P100) were sensitive to i) the temporal dynamics of crossmodal interactions, and ii) the relevance of these sensory signals for behaviour.

Conclusion

Notably, the P50 amplitude was greatest in the VTd condition, suggesting that presentation of relevant visual information for upcoming movement modulates somatosensory processing in modality‐specific cortical regions, as early as the primary somatosensory cortex (SI).
Nitrogen‐Doped Carbon–Copper Nanohybrids as Electrocatalysts in H2O2 and Glucose Sensing
Authors: Wei Chengzhen , Liu Yuanying , Li Xinran , Zhao Junhong , Ren Zhen , Pang Huan
Published: January 2014

Nitrogen‐doped carbon–copper nanohybrids are prepared through the calcination of cis‐Cu(gly)2⋅x H2O nanofibers and trans‐Cu(gly)2⋅x H2O nanoplates in Ar gas. Benefitting from nanoporous structures and high nitrogen contents, the nitrogen‐doped carbon–copper nanohybrids can be used to modify electrodes, which show effective non‐enzymatic hydrogen peroxide and glucose sensing capabilities. The electrode modified with nitrogen‐doped carbon–copper nanohybrid plates is especially effective for glucose sensing, as it shows a low detection limit of 5 μM, good sensitivity of 223.6 μA mM−1 cm−2, and excellent selectivity.
Modification of Extended Open Frameworks with Fluorescent Tags for Sensing Explosives: Competition between Size Selectivity and Electron Deficiency
Authors: Gole Bappaditya , Bar Arun Kumar , Mukherjee Partha Sarathi
Published: January 2014

Three new electron‐rich metal–organic frameworks (MOF‐1–MOF‐3) have been synthesized by employing ligands bearing aromatic tags. The key role of the chosen aromatic tags is to enhance the π‐electron density of the luminescent MOFs. Single‐crystal X‐ray structures have revealed that these MOFs form three‐dimensional porous networks with the aromatic tags projecting inwardly into the pores. These highly luminescent electron‐rich MOFs have been successfully utilized for the detection of explosive nitroaromatic compounds (NACs) on the basis of fluorescence quenching. Although all of the prepared MOFs can serve as sensors for NACs, MOF‐1 and MOF‐2 exhibit superior sensitivity towards 4‐nitrotoluene (4‐NT) and 2,4‐dinitrotoluene (DNT) compared to 2,4,6‐trinitrotoluene (TNT) and 1,3,5‐trinitrobenzene (TNB). MOF‐3, on the other hand, shows an order of sensitivity in accordance with the electron deficiencies of the substrates. To understand such anomalous behavior, we have thoroughly analyzed both the steady‐state and time‐resolved fluorescence quenching associated with these interactions. Determination of static Stern–Volmer constants (KS) as well as collisional constants (KC) has revealed that MOF‐1 and MOF‐2 have higher KS values with 4‐NT than with TNT, whereas for MOF‐3 the reverse order is observed. This apparently anomalous phenomenon was well corroborated by theoretical calculations. Moreover, recyclability and sensitivity studies have revealed that these MOFs can be reused several times and that their sensitivities towards TNT solution are at the parts per billion (ppb) level.
Hydrosilylation Induced by N→Si Intramolecular Coordination: Spontaneous Transformation of Organosilanes into 1‐Aza‐Silole‐Type Molecules in the Absence of a Catalyst
Authors: Novák Miroslav , Dostál Libor , Alonso Mercedes , De Proft Frank , Růžička Aleš , Lyčka Antonín , Jambor Roman
Published: January 2014

Our attempts to synthesize the N→Si intramolecularly coordinated organosilanes Ph2L1SiH (1 a), PhL1SiH2 (2 a), Ph2L2SiH (3 a), and PhL2SiH2 (4 a) containing a CHN imine group (in which L1 is the C,N‐chelating ligand {2‐[CHN(C6H3‐2,6‐iPr2)]C6H4}− and L2 is {2‐[CHN(tBu)]C6H4}−) yielded 1‐[2,6‐bis(diisopropyl)phenyl]‐2,2‐diphenyl‐1‐aza‐silole (1), 1‐[2,6‐bis(diisopropyl)phenyl]‐2‐phenyl‐2‐hydrido‐1‐aza‐silole (2), 1‐tert‐butyl‐2,2‐diphenyl‐1‐aza‐silole (3), and 1‐tert‐butyl‐2‐phenyl‐2‐hydrido‐1‐aza‐silole (4), respectively. Isolated organosilicon amides 1–4 are an outcome of the spontaneous hydrosilylation of the CHN imine moiety induced by N→Si intramolecular coordination. Compounds 1–4 were characterized by NMR spectroscopy and X‐ray diffraction analysis. The geometries of organosilanes 1 a–4 a and their corresponding hydrosilylated products 1–4 were optimized and fully characterized at the B3LYP/6‐31++G(d,p) level of theory. The molecular structure determination of 1–3 suggested the presence of a SiN double bond. Natural bond orbital (NBO) analysis, however, shows a very strong donor–acceptor interaction between the lone pair of the nitrogen atom and the formal empty p orbital on the silicon and therefore, the calculations show that the SiN bond is highly polarized pointing to a predominantly zwitterionic Si+N− bond in 1–4. Since compounds 1–4 are hydrosilylated products of 1 a–4 a, the free energies (ΔG298), enthalpies (ΔH298), and entropies (ΔH298) were computed for the hydrosilylation reaction of 1 a–4 a with both B3LYP and B3LYP‐D methods. On the basis of the very negative ΔG298 values, the hydrosilylation reaction is highly exergonic and compounds 1 a–4 a are spontaneously transformed into 1–4 in the absence of a catalyst.
Perkin’s and Caro’s Mauveine in Queen Victoria’s Lilac Postage Stamps: A Chemical Analysis
Authors: Conceição Oliveira Maria da , Dias Ana , Douglas Peter , Seixas de Melo J. Sérgio
Published: January 2014

Mauveine, a chemical icon, is no longer commercially available. If nowadays one wanted to have a sample of the original Perkin, or Caro, mauveine, and see its colour, where would one find it? The answer is on UK Victorian 6d postage stamps from 1867–1880. This was found from a comparison with historical samples of mauveine, from both William Perkin and a Heinrich Caro sample (here analysed for the first time). These have distinctly different compositions and this was used to identify the origin of mauveine in the postage stamps, with evidence found for mauveine made by both Perkin’s and Caro’s synthesis.
Coordination Chemistry of Cyclopropenylidene‐Stabilized Phosphenium Cations: Synthesis and Reactivity of Pd and Pt Complexes
Authors: Kozma Ágnes , Deden Tobias , Carreras Javier , Wille Christian , Petuškova Jekaterina , Rust Jörg , Alcarazo Manuel
Published: January 2014

A straightforward synthesis of cyclopropenylidene‐stabilized phosphenium cations 1 a–g through the reaction of [(iPr2N)2C3+Cl]BF4 with secondary phosphines is described. Their donor ability was evaluated by analysis of the CO stretching frequency in Rh complexes [RhCl(CO)L2](BF4)2 and electrochemical methods. The cyclopropenium ring induces a phosphite‐type behavior that can be tuned by the other two substituents attached to the phosphorus atom. Despite of the positive charge that they bear, phosphenium cations 1 a–g still act as two‐electron donor ligands, forming adducts with PdII and PtII precursors. Conversely, in the presence of Pd0 species, an oxidative insertion of the Pd atom into the Ccarbene–phosphorus bond takes place, providing dimeric structures in which each Pd atom is bonded to a cyclopropenyl carbene while two dialkyl/diaryl phosphide ligands serve as bridges between the two Pd centers. The catalytic performance of the resulting library of PtII complexes was tested; all of the cationic phosphines accelerated the prototype 6‐endo‐dig cyclization of 2‐ethynyl‐1,1′‐biphenyl to afford pentahelicene. The best ligand 1 g was used in the synthesis of two natural products, chrysotoxene and epimedoicarisoside A.
Hybridization of a Flexible Cyclooctatetraene Core and Rigid Aceneimide Wings for Multiluminescent Flapping π Systems
Authors: Yuan Chunxue , Saito Shohei , Camacho Cristopher , Kowalczyk Tim , Irle Stephan , Yamaguchi Shigehiro
Published: January 2014

The hybridization of flexible and rigid π‐conjugated frameworks is a potent concept for producing new functional materials. In this article, a series of multifluorescent flapping π systems that combine a flexible cyclooctatetraene (COT) core and rigid aceneimide wings with various π‐conjugation lengths has been designed and synthesized, and their structure/properties relationships have been investigated. Whereas these molecules have a V‐shaped bent conformation in the ground state, the bent structure changes to a planar conformation in the lowest excited singlet (S1) state irrespective of the lengths of the aceneimide wings. However, the fluorescence behavior in solution is distinct between the naphthaleneimide system and the anthraceneimide system. The former has a nonemissive S1 state owing to the significant contribution of the antiaromatic character of the planar COT frontier molecular orbitals, thereby resulting in complete fluorescence quenching in solution. In contrast, the latter anthraceneimide system shows an intense emission, which is ascribed to the planar but distorted S1 state that shows the allowed transition between the π‐molecular orbitals delocalized over the COT core and the acene wings. The other characteristic of these π systems is the significantly redshifted fluorescence in the crystalline state relative to their monomer fluorescence. The relationship between the packing structures and the fluorescence properties was investigated by preparing a series of hybrid π systems with different sizes of substituents on the imide moieties, which revealed the effect of the twofold π‐stacked structure of the V‐shaped molecules on the large bathochromic shift in emission.
Total Synthesis of Chiriquitoxin, an Analogue of Tetrodotoxin Isolated from the Skin of a Dart Frog
Authors: Adachi Masaatsu , Imazu Takuya , Sakakibara Ryo , Satake Yoshiki , Isobe Minoru , Nishikawa Toshio
Published: January 2014

The first total synthesis of chiriquitoxin, the most structurally complex analogue of tetrodotoxin isolated from a Costa Rican dart frog, has been accomplished from a newly designed intermediate for a variety of tetrodotoxin derivatives. The synthesis includes the third total synthesis of tetrodotoxin in this laboratory, and its intermediate was transformed into chiriquitoxin by a stereocontrolled aldol reaction with a D‐camphor‐derived lactone for installation of the unique side chain, and a new deprotection of methylthiomethyl (MTM) ether by using a Pummerer rearrangement.
Plasmonic Nanobiosensor with Chain Reaction Amplification Mechanism
Authors: Recco Lucas C. , Tokarev Ihor , Minko Sergiy , Pedrosa Valber A.
Published: January 2014

Herein we demonstrate a plasmonic nanobiosensor that explores chain reaction amplification mechanisms to transduce chemical signals released in biocatalytic reactions, turning optical signals into a visual spectral range. The sensor has a very simple design: gold nanoparticles resting in the surface of a grafted P2VP film. Changes in the gold nanoparticles’ position causes changes in the plasmon coupling mode. This is detected by means of a maximum absorbance shift.
ChemInform Abstract: Gold Network Structures in Rhombohedral and Monoclinic Sr2Au6(Au,T)3 (T: Zn, Ga). A Transition via Relaxation.
Authors: Mishra Trinath , Lin Qisheng , Corbett John D.
Published: January 2014

Sr2Au6(Au3‐xMx) (M: Zn, Ga) samples with 1 ≤ x ≤ 3 are prepared by reaction of the elements (sealed Ta tubes, 800 °C, 10 h).
ChemInform Abstract: Color‐Tunable and White Luminescence Properties via Energy Transfer in Single‐Phase KNaCa2(PO4)2:A (A: Ce3+, Eu2+, Tb3+, Mn2+, Sm3+) Phosphors.
Authors: Geng Dongling , Shang Mengmeng , Zhang Yang , Lian Hongzhou , Lin Jun
Published: January 2014

The title phosphors are synthesized by a Pechini‐type sol—gel method followed by calcination in air at 950 °C for 4 h.
ChemInform Abstract: From REZnSn to REZnSnH1.5 (RE: Pr, Nd) — Inducing Ferromagnetism Through Hydrogenation.
Authors: Reker Bastian , Chevalier Bernard , Niehaus Oliver , Rodewald Ute Ch. , Poettgen Rainer
Published: January 2014

Polycrystalline PrZnSn (I) and NdZnSn (II) are prepared by induction melting of the elements in sealed tantalum tubes (1.
ChemInform Abstract: Magnetic Structure and Electromagnetic Properties of LnCrAsO with a ZrCuSiAs‐Type Structure (Ln: La, Ce, Pr, and Nd).
Authors: Park Sang‐Won , Mizoguchi Hiroshi , Kodama Katsuaki , Shamoto Shin‐ichi , Otomo Toshiya , Matsuishi Satoru , Kamiya Toshio , Hosono Hideo
Published: January 2014

LnCrAsO (Ln: La, Ce, Pr, Nd) is prepared by solid state reaction of stoichiometric mixtures of LnAs, Cr, and Cr2O3 (evacuated silica tube, 1273 K, 20 h).
ChemInform Abstract: Slow Spin Dynamics Between Ferromagnetic Chains in a Pure‐Inorganic Framework.
Authors: David Renald , Kabbour Houria , Colis Silviu , Mentre Olivier
Published: January 2014

The new compound BaCo2 (As3O6)2·2H2O is prepared from a mixture of BaCO3, CoCl2, As2O3, H2O, and N2H4 (autoclave, 493 K, 72 h) and characterized by single crystal XRD, magnetic measurements, and DFT calculations.
ChemInform Abstract: The System Ba—Zn—Sn at 500 °C: Phase Equilibria, Crystal and Electronic Structure of Ternary Phases.
Authors: Romaka V. V. , Falmbigl M. , Grytsiv A. , Rogl P.
Published: January 2014

Phase relations in the Ba‐poor part of the ternary Ba—Zn—Sn system at 500 °C are established by arc melting of the elements with an excess of Ba of 3 wt% (1.
ChemInform Abstract: Mechanistic Study of the Rhodium‐Catalyzed [3 + 2 + 2] Carbocyclization of Alkenylidenecyclopropanes with Alkynes.
Authors: Yu Haizhu , Lu Qianqian , Dang Zhimin , Fu Yao
Published: January 2014

Two different mechanisms of the reaction are investigated by theoretical calculations using density functional theory.
ChemInform Abstract: Discovery of Neuritogenic Compound Classes Inspired by Natural Products.
Authors: Dakas Pierre‐Yves , Parga Juan A. , Hoeing Susanne , Schoeler Hans R. , Sterneckert Jared , Kumar Kamal , Waldmann Herbert
Published: January 2014

Two novel neuritogenic compound classes are accessible based on an enantioselective [3+2]‐annulation of cyclopentenones with allene‐derived zwitterions.
ChemInform Abstract: Silver‐Catalyzed Intramolecular Hydroamination of Alkynes with Trichloroacetimidates.
Authors: Wong Valerie H. L. , Hor T. S. Andy , Hii King Kuok
Published: January 2014

The title reaction is achieved for the first time, whereby the nature of the counterion, solvent, and ligand are found to have profound effects on catalytic turnover and selectivity.
ChemInform Abstract: Highly Diastereoselective Radical Cyclizations of Chiral Sulfinimines.
Authors: Rochette Elise M. , Lewis William , Dossetter Al G. , Stockman Robert A.
Published: January 2014

A tin hydride and AIBN mediated intramolecular cyclization of alkyl and aryl radicals derived from halides and chiral sulfinimines is presented.
ChemInform Abstract: C—H Modification of 2‐Azaadamantane: Synthesis of C5‐Functionalized Azados for Advanced Use.
Authors: Sasano Yusuke , Nishiyama Tomohiro , Tomizawa Masaki , Shibuya Masatoshi , Iwabuchi Yoshiharu
Published: January 2014

Two substituted 2‐aza‐adamantane N‐oxyls of type ADAB are prepared and tested as catalysts for the oxidation of alcohols.
ChemInform Abstract: A Highly Active Cyclometallated Iridium Catalyst for the Hydrogenation of Imines.
Authors: Villa‐Marcos Barbara , Tang Weijun , Wu Xiaofeng , Xiao Jianliang
Published: January 2014

The novel catalyst is highly active and selective for imino bonds, with a wide variety of imines being hydrogenated in less than 1 hour.
ChemInform Abstract: An Efficient Oxidative Cross‐Coupling Reaction Between C—H and N—H Bonds. A Transition‐Metal‐Free Protocol at Room Temperature.
Authors: Wu Yinuo , Kwong Fuk Yee , Li Pengfei , Chan Albert S. C.
Published: January 2014

The DDQ promoted oxidative coupling of 1,3‐diarylpropenes with N‐heterocycles and amines provides allylic amines under mild reaction conditions.
ChemInform Abstract: Rhodium(III)‐Catalyzed ortho‐Olefination of Aryl Phosphonates.
Authors: Chary Bathoju Chandra , Kim Sunggak
Published: January 2014

In the title reaction, the phosphonic ester as well as the phosphonic diamide moiety are utilized as directing groups.
ChemInform Abstract: Reactions of Epoxides with 3,3,4,4‐Tetraethoxybut‐1‐yne Acetylide: Selective Formation of Propargylic and Homopropargylic Alcohols.
Authors: Holmelid Bjarte , Sydnes Leiv K.
Published: January 2014

Propargylic alcohols (III) are obtained via an oxirane to aldehyde rearrangement before the addition of the acetylide takes place.
ChemInform Abstract: Free‐Radical Variant for the Synthesis of Functionalized 1,5‐Diketones.
Authors: Goh Kelvin Kau Kiat , Kim Sunggak , Zard Samir Z.
Published: January 2014

This effective method allows the facile and direct preparation of various functionalized diketones, which can be used for the synthesis of fused pyridine derivatives.
ChemInform Abstract: Metal‐Free Direct C—H Perfluoroalkylation of Arenes and Heteroarenes Using a Photoredox Organocatalyst.
Authors: Cui Lei , Matusaki Yoko , Tada Norihiro , Miura Tsuyoshi , Uno Bunji , Itoh Akichika
Published: January 2014

The best results are obtained when the irradiation is carried out with only one lamp instead of four lamps.
ChemInform Abstract: Asymmetric Aminocatalytic Michael Addition of Cyclopropane‐Containing Aldehydes to Nitroalkenes.
Authors: Reitel Kaert , Lippur Kristin , Jaerving Ivar , Kudrjasova Marina , Lopp Margus , Kanger Tonis
Published: January 2014

Optimized conditions allow the synthesis of Michael adducts (III) with high enantioselectivity.
ChemInform Abstract: Fast and Selective Iron‐Catalyzed Transfer Hydrogenations of Aldehydes.
Authors: Wienhoefer Gerrit , Westerhaus Felix A. , Junge Kathrin , Beller Matthias
Published: January 2014

A wide range of functional groups including other reducible moieties is tolerated in this reduction.
ChemInform Abstract: Synthesis of Z‐Alkenes from Rh(I)‐Catalyzed Olefin Isomerization of β,γ‐Unsaturated Ketones.
Authors: Zhuo Lian‐Gang , Yao Zhong‐Ke , Yu Zhi‐Xiang
Published: January 2014

The title synthesis is applicable for a broad range of aromatic and aliphatic substituted ketones.
ChemInform Abstract: Preparation of α‐Imino Aldehydes by [1,3]‐Rearrangements of O‐Alkenyl Oximes.
Authors: Kontokosta Dimitra , Mueller Daniel S. , Wang Heng‐Yen , Anderson Laura L.
Published: January 2014

The α‐imino aldehydes obtained after the rearrangement reaction can also be directly converted to imino esters (VI) and (VII) by a subsequent Horner‐Wadsworth‐Emmons olefination.
ChemInform Abstract: Simple and Stereocontrolled Preparation of Benzoylated Phenylalanine Using Friedel—Crafts Reaction in Trifluoromethanesulfonic Acid for Photoaffinity Labeling.
Authors: Murai Yuta , Wang Lei , Muto Yasuyuki , Sakihama Yasuko , Hashidoko Yasuyuki , Hatanaka Yasumaru , Hashimoto Makoto
Published: January 2014

The stereocontrolled Friedel‐Crafts benzoylation of chiral phenylalanine derivatives is described.
ChemInform Abstract: γ‐Substituted Butanolides from Cyclopropane Hemimalonates: An Expedient Synthesis of Natural (R)‐Dodecan‐4‐olide (IX).
Authors: Grover Huck K. , Emmett Michael R. , Kerr Michael A.
Published: January 2014

This efficient approach affords a wide range of different substituted lactone derivatives via a tandem cyclopropane hemimalonate reorganization/dealkoxycarbonylation reaction sequence.
ChemInform Abstract: Highly Active Catalysts of Bisphosphine Oxides for Asymmetric Heck Reaction.
Authors: Hu Jian , Lu Yunpeng , Li Yongxin , Zhou Jianrong
Published: January 2014

The utilization of chiral biphosphine oxides as ligand in asymmetric heck reactions of cycloalkenes, furanes, pyranes, and pyrrol systems is presented.
ChemInform Abstract: Synthesis and Photophysical Properties of Push—Pull Structures Incorporating Diazines as Attracting Part with a Fluorene Core.
Authors: Denneval Charline , Moldovan Oana , Baudequin Christine , Achelle Sylvain , Baldeck Patrice , Ple Nelly , Darabantu Mircea , Ramondenc Yvan , Darabantu Mircea , Ramondenc Yvan
Published: January 2014

Several new push—pull fluorene derivatives such as (IV), (VI), and (VII) are prepared in order to test their photophysical properties.
ChemInform Abstract: The Di‐t‐butylsilylene Protecting Group as a Bridging Unit in Linear and Macrocyclic Bis‐Malonates for the Regioselective Multifunctionalization of C60.
Authors: Guerra Sebastiano , Trinh Thi Minh Nguyet , Schillinger Franck , Muhlberger Lucie , Sigwalt David , Holler Michel , Nierengarten Jean‐Francois
Published: January 2014

This describes the functionalization of fullerenes by double Bingel cyclopropanation reaction with tethered bis‐malonates.
ChemInform Abstract: Enantioselective Construction of Spirooxindole Derivatives: Asymmetric [3 + 2] Cyclization of Isothiocyanatooxindoles with Allenic Esters or 2‐Butynedioic Acid Diesters.
Authors: Du Dan , Jiang Yu , Xu Qin , Shi Min
Published: January 2014

The reactions are catalyzed by a novel Cinchona alkaloid‐derived organocatalyst and different spirocyclic products are obtained depending on the reaction conditions and the ratios of reagents.
ChemInform Abstract: Application of Sulfuryl Chloride for the Quick Construction of β‐Chlorotetrahydrofuran Derivatives from Homoallylic Alcohols under Mild Conditions.
Authors: Zeng Xianghua , Miao Chengxia , Wang Shoufeng , Xia Chungu , Sun Wei
Published: January 2014

The 5‐endo chlorocycloetherification proceeds rapidly under catalyst‐free‐conditions to give β‐chlorotetrahydrofurans in high yields.
ChemInform Abstract: Imidazolium‐Salt‐Functionalized Ionic‐CNT‐Supported Ru—Carbene/Palladium Nanoparticles for Recyclable Tandem Metathesis/Hydrogenation Reactions in Ionic Liquids.
Authors: Lee Sujin , Shin Ju Yeon , Lee Sang‐gi
Published: January 2014

Ruthenium carbene and palladium nanoparticles are immobilized onto the same imidazolium‐functionalized ionic carbon nanotubes and the catalyst is showing high effectivity in tandem metathesis/hydrogenation reaction in an ionic liquid.
ChemInform Abstract: The Preparation of Various New Heterocyclic Compounds via Cyclization of Substituted Derivatives of Phenacyl Esters of Hydrazonoacetic Acid.
Authors: Melnicky Radek , Grepl Martin , Lycka Antonin , Bertolasi Valerio , Kvapil Lubomir , Dvorakova Barbora , Hradil Pavel
Published: January 2014

The acid‐mediated Fischer‐indole synthesis type cyclization of hydrazones (I) and (V) is studied resulting in the formation of indoles (II) and (VI).
ChemInform Abstract: An Organocatalytic Asymmetric Sequential Allylic Alkylation—Cyclization of Morita—Baylis—Hillman Carbonates and 3‐Hydroxyoxindoles.
Authors: Wang Qi‐Lin , Peng Lin , Wang Fei‐Ying , Zhang Ming‐Liang , Jia Li‐Na , Tian Fang , Xu Xiao‐Ying , Wang Li‐Xin
Published: January 2014

The first organocatalytic asymmetric cyclization of the title compounds is presented.
ChemInform Abstract: Reactions of Some Pyrazole‐3‐carboxylic Acids and Carboxylic Acid Chlorides with Various O‐ and N‐Nucleophiles.
Authors: Ilhan Ilhan Oezer , Caglayan Ayse , Oenal Zuelbiye , Akkoc Senem , Cadir Mehmet
Published: January 2014

Convenient methods for the efficient synthesis of previously unknown pyrazole‐3‐hydrazides, pyrazolo‐[3,4‐d]pyradizin‐ones, pyrazole‐3‐carboxylates, pyrazole‐3‐carboxamide, and pyrazole‐3‐urea derivatives are developed.
ChemInform Abstract: Synthesis, Characterization and Antiinflammatory Activity of Novel Pyrazolyl Ketoamides.
Authors: Mahaveer P. , Kulkarni R. G. , Radakrishna P. , Chandrashekar V. M. , Achaiah G.
Published: January 2014

The title compounds (IV) are obtained by coupling of 5‐aminopyrazole with substituted α‐keto acids and screened for their antiinflammatory activities.
ChemInform Abstract: Intramolecular Arylation of Amino Acid Enolates.
Authors: Atkinson Rachel C. , Leonard Daniel J. , Maury Julien , Castagnolo Daniele , Volz Nicole , Clayden Jonathan
Published: January 2014

The treatment of 1‐cyanoethyl ureas (I) with sBuLi leads to iminohydantoins (II) as a result of an aryl migration and a cyclization.
ChemInform Abstract: Ionic Liquid Mediated Synthesis of Some Novel Fluoro Isoxazolidine and Isoxazoline Derivatives Using N‐Benzyl Fluoro Nitrone via Cycloaddition Reaction and Their Antimicrobial Activities.
Authors: Chakraborty Bhaskar , Samanta Amalesh , Luitel Govinda Prasad , Khatun Nasima
Published: January 2014

The compounds (IVb), (Vb), and (VIIb) show good inhibition against some bacterial cell‐lines (Shigella dysentery 1 and Pseudomonas AMRI 100) compared to the standard Amoxicillin.
ChemInform Abstract: Regioselective Conjugate Addition of Nitriles to α,β‐Unsaturated Imines: Synthesis of Fluorinated Primary Enamines and 2‐Aminopyridine Derivatives.
Authors: Fernandez de Troconiz Guillermo , Ochoa de Retana Ana M. , Pascual Sergio , Ezpeleta Jose M. , Palacios Francisco
Published: January 2014

Base‐mediated treatment of the imines (I) with the nitriles (I) and (V) is found to allow convenient and regioselective formation of stable primary enamines.
ChemInform Abstract: Tungstophosphoric Acid Catalyzed Synthesis of N‐Sulfonyl‐1,2,3,4‐tetrahydroisoquinoline Analogues
Authors: Pingaew Ratchanok , Prachayasittikul Supaluk , Ruchirawat Somsak , Prachayasittikul Virapong
Published: January 2014

via a modified Pictet—Spengler reaction
ChemInform Abstract: A Mild Synthesis of [1,2,4]Triazolo[4,3‐a]pyridines.
Authors: Schmidt Michael A. , Qian Xinhua
Published: January 2014

The electronic and steric properties of the hydrazine and imidate strongly impact the rate of the reaction.
ChemInform Abstract: 7,9,12b‐Triazabenzo[a]aceanthrylen‐8‐one, the First Representative of a Novel Pentacyclic Ring System and Its Biological Activities.
Authors: Puzik Andreas , Bracher Franz
Published: January 2014

The novel canthin‐4‐one derivative (VI) bearing an annulated pyridine ring is synthetically accessible by a four‐step approach and shows selective cytotoxic activity against Gram‐positive bacteria.
ChemInform Abstract: Claisen‐Schmidt Condensation in Solvent‐Free Conditions via the Use of Microwave Irradiation and Pestle/Mortar.
Authors: Mogilaiah K. , Chandra A. Vinay , Praveena D.
Published: January 2014

Both the methods are attractive due to their simplicity, ease of workability, enhanced yields, reduced reaction time period and practical applicability.
ChemInform Abstract: N‐Heterocyclic Carbene‐Catalyzed Stereoselective Cascade Reaction: Synthesis of Functionalized Tetrahydroquinolines.
Authors: Zhang Hai‐Rui , Dong Zhen‐Wen , Yang Yu‐Jie , Wang Ping‐Luan , Hui Xin‐Ping
Published: January 2014

The construction of chiral functionalized tetrahydroquinolines with three consecutive stereogenic centers is achieved by the first NHC‐catalyzed stereoselective aza‐Michael‐Michael‐lactonization cascade reaction of aminophenylenones with bromoenals.
ChemInform Abstract: Stereoselective Amine Addition of Six‐Membered Cyclic Nitronates Promoted by Silyl Triflate.
Authors: Mikhaylov Andrey A. , Dilman Alexander D. , Khomutova Yulia A. , Arkhipov Dmitry E. , Korlyukov Alexander A. , Ioffe Sema L.
Published: January 2014

The reaction products occur in different conformations depending on the substitution pattern.
ChemInform Abstract: An Efficient One‐Pot Synthesis of Pyrazolyl‐[1,2,4]triazolo[3,4‐b][1,3,4]thiadiazin‐6‐yl‐2H‐pyran‐2‐one Derivatives via Multicomponent Approach and Their Potential Antimicrobial and Nematicidal Activities.
Authors: Penta Santhosh , Gadidasu Kranthi Kumar , Basavoju Srinivas , Rao Vedula Rajeswar
Published: January 2014

Title compounds (IV) and (VI) are synthesized and evaluated for their in vitro antimicrobial activity against both gram‐positive and gram‐negative bacteria as well as their antifungal and nematicidal activity.
ChemInform Abstract: Potassium (E)‐Alkenylaryltrifluoroborates: Orthogonal Functionalization of Haloaryltrifluoroborates via Heck—Mizoroki Reaction.
Authors: Song Jung Ho , Kim Taejung , Lee Jae Wook , Moon Soo‐Yeon , Kim Won‐Suk , Ham Jungyeob
Published: January 2014

The target compounds are prepared from arylolefins or activated olefins.
ChemInform Abstract: Antimycobacterial Agent, (E)‐Phytol and Lauric Amide from the Plant Lagascea mollis.
Authors: Bhattacharya Asish K. , Rana Kalpeshkumar C.
Published: January 2014

isolation and characterization of the antimycobacterial diterpene alcohol, (E)‐phytol (I), and lauric amide
ChemInform Abstract: A Facile Synthesis of N/C‐Terminal Selenourea Tethered Glycosylated Amino Acids
Authors: Sureshbabu Vommina V. , Vasantha B. , Madhu C.
Published: January 2014

via coupling of isoselenocyanates (II) or (IV) with O‐protected glycosylamines (I)
ChemInform Abstract: Practical Silyl Protection of Ribonucleosides.
Authors: Blaisdell Thomas P. , Lee Sunggi , Kasaplar Pinar , Sun Xixi , Tan Kian L.
Published: January 2014

A selective silylation of the 3′‐ or 2′‐hydroxyl groups is achieved by choosing the enantiomer of the catalyst.
ChemInform Abstract: DNA Modification under Mild Conditions by Suzuki—Miyaura Cross‐Coupling for the Generation of Functional Probes.
Authors: Lercher Lukas , McGouran Joanna F. , Kessler Benedikt M. , Schofield Christopher J. , Davis Benjamin G.
Published: January 2014

A new efficient method for Pd‐catalyzed Suzuki—Miyaura cross‐coupling to iododeoxyuridine in DNA is described.
ChemInform Abstract: Low‐Temperature Solution Processing of Mesoporous Metal—Sulfide Semiconductors as Light‐Harvesting Photoanodes.
Authors: O'Mahony Flannan T. F. , Cappel Ute B. , Tokmoldin Nurlan , Lutz Thierry , Lindblad Rebecka , Rensmo Haakan , Haque Saif A.
Published: January 2014

Mesoporous films of highly crystalline Sb2S3 are prepared from a precursor paste of Sb(S2CO‐Et)3, hexylamine, and chlorobenzene by annealing at 120 °C.
ChemInform Abstract: Nickel Dichalcogenide Hollow Spheres: Controllable Fabrication, Structural Modification, and Magnetic Properties.
Authors: Ma Wei , Guo Yanfeng , Liu Xiaohe , Zhang Dan , Liu Tao , Ma Renzhi , Zhou Kechao , Qiu Guanzhou
Published: January 2014

NiS2 hollow spheres are hydrothermally synthesized from a mixture of Ni(NO3)2, L‐cysteine, urea, and H2O (autoclave, 140 °C, 24 h).
ChemInform Abstract: Complexes with Nitrogen‐Centered Radical Ligands: Classification, Spectroscopic Features, Reactivity, and Catalytic Applications
Authors: Suarez Alma I. Olivos , Lyaskovskyy Volodymyr , Reek Joost N. H. , van der Vlugt Jarl Ivar , de Bruin Bas
Published: January 2014

Review: 106 refs.
ChemInform Abstract: Transition‐Metal‐Catalyzed Laboratory‐Scale Carbon—Carbon Bond‐Forming Reactions of Ethylene
Authors: Saini Vaneet , Stokes Benjamin J. , Sigman Matthew S.
Published: January 2014

Review: 74 refs.
ChemInform Abstract: C—N Bond Forming Cross‐Coupling Reactions: An Overview
Authors: Bariwal Jitender , Van der Eycken Erik
Published: January 2014

Review: 50 refs.
ChemInform Abstract: Chemical Reactivity and Long‐Range Transport Potential of Polycyclic Aromatic Hydrocarbons. A review.
Authors: Keyte Ian J. , Harrison Roy M. , Lammel Gerhard
Published: January 2014

Review: 472 refs.
ChemInform Abstract: Primary and Secondary Amine‐(Thio)ureas and Squaramides and Their Applications in Asymmetric Organocatalysis
Authors: Tsakos Michail , Kokotos Christoforos G.
Published: January 2014

Review: [138 refs.]
ChemInform Abstract: Recent Developments in Amide Synthesis: Direct Amidation of Carboxylic Acids and Transamidation Reactions
Authors: Lanigan Rachel M. , Sheppard Tom D.
Published: January 2014

Review: 66 refs.
ChemInform Abstract: Award‐Winning Organometallic Chemistry: The 2013 Yao Zeng Award in Organometallic Chemistry
Authors: Gladysz John A.
Published: January 2014

Review: 4 refs.
ChemInform Abstract: Tuning Acid‐base Cooperativity to Create Next Generation Silica‐supported Organocatalysts
Authors: Brunelli Nicholas A. , Jones Christopher W.
Published: January 2014

Review: 101 refs.
ChemInform Abstract: Rational Design of Self‐assembled Proteins and Peptides for Nano‐ and Micro‐sized Architectures
Authors: Matsuurua Kazunori
Published: January 2014

Review: 100 refs.
ChemInform Abstract: Gold Catalysis for Organic Synthesis. Part 2.
Authors: Dean Toste F.
Published: January 2014

Review: introduction to a series of review articles
ChemInform Abstract: Sesquiterpenyl Indoles
Authors: Marcos Isidro S. , Moro Rosalina F. , Costales Isabel , Basabe Pilar , Diez David
Published: January 2014

Review: classification, biosynthetic and synthetic approaches; 72 refs.
ChemInform Abstract: Magnetic Characterization of Exchange Coupled Ultrathin Magnetic Multilayers by Ferromagnetic Resonance Technique
Authors: Aktas Bekir , Topkaya Ramazan , Erkovan Mustafa , Ozdemir Mustafa
Published: January 2014

Review: 53 refs.
ChemInform Abstract: Magnetic and Magnetoresistive Properties of Thin Films Patterned by Self‐assembling Polystyrene Nanopheres
Authors: Coisson Marco , Celegato Federica , Tiberto Paola , Vinai Franco , Boarino Luca , De Leo Natascia
Published: January 2014

Review: 41 refs.
ChemInform Abstract: From Protein Engineering to Immobilization: Promising Strategies for the Upgrade of Industrial Enzymes
Authors: Singh Raushan Kumar , Tiwari Manish Kumar , Singh Ranjitha , Lee Jung‐Kul
Published: January 2014

Review: 279 refs.
ChemInform Abstract: Biosensors as Bio‐based Materials in Chemical Analysis: a Review
Authors: Pisoschi Aurelia Magdalena
Published: January 2014

Review: 153 refs.
ChemInform Abstract: Host‐guest Supramolecular Chemistry at Solid‐liquid Interface: An Important Strategy for Preparing Two‐dimensional Functional Nanostructures
Authors: Zhang Xue Mei , Zeng Qing Dao , Wang Chen
Published: January 2014

Review: 113 refs.
ChemInform Abstract: Density Functional Theory Methods for Characterization of Porous Materials
Authors: Landers John , Gor Gennady Yu. , Neimark Alexander V.
Published: January 2014

Review: 209 refs.
Synthesis, Characterization and Cytotoxicity of (η6‐p‐cymene)ruthenium(II) Complexes of α‐Amino Acids
Authors: Egbewande Folake A. , Paul Lydia E. H. , Therrien Bruno , Furrer Julien
Published: January 2014

Arene ruthenium complexes of α‐amino acids, obtained by mixing aqueous solutions of [(η6‐p‐cymene)RuCl2]2in the presence of AgCF3SO3with various amino acids, have been studied at 37 °C using NMR spectroscopy and electrospray ionization mass spectrometry (ESI‐MS). Small hydrophobic α‐amino acid anions were found to form bidentateN,O‐chelate complexes, whereas α‐amino acids with coordinating side chains (e.g. serine, aspartic acid, histidine) acted as tridentate ligands. For many amino acids, more than two chelate complexes were formed. Presumably, complexes with the general formula [(η6‐p‐cymene)Ru(AA)2]n+and bridged complexes with the general formula [{(η6‐p‐cymene)Ru}2(μ‐AA)2(μ‐OH)]+were observed together with the expected bi‐ and tridentate chelate complexes. All complexes, isolated as triflate salts, were evaluated for their in vitro anticancer activity against the human ovarian cancer cell line A2780 and its cisplatin‐resistant mutant A2780cisR. All complexes were found to be highly cytotoxic, with IC50values ranging from 0.16–19.8 μM. Interestingly, all complexes were selectivity active against A2780 cells relative to the A2780cisR variants, indicating a distinct mechanism of action that differs from that of many previously reported cytotoxic ruthenium complexes. No direct correlation between the kinetics of complex formation and cytotoxicity was apparent, suggesting that other physicochemical parameters such as complex stability and ligand exchange kinetics may play important roles in the biological activity.
A Convenient Approach to N‐(Di‐tert‐butylphosphanyl)‐ and N‐(Di‐tert‐butylphosphoroselenoyl)formamidinium Salts: Carbene Precursors
Authors: Marchenko Anatoliy , Koidan Georgyi , Hurieva Anastasiya , Savateev Aleksandr , Rozhenko Alexander B. , Sotiropoulos Jean‐Marc , Shishkina Svitlana V. , Shishkin Oleg V. , Kostyuk Aleksandr
Published: January 2014

The reactions of (di‐tert‐butylphosphanyl)amines and P,P‐di‐tert‐butylphosphinoselenoic amides with Alder's dimer were studied. For di‐tert‐butylphosphanylamines, the reaction proceeds by primary electrophilic attack of Alder's dimer at the phosphorus atom to afford a dicationic salt 3. The deprotonation of 3 led to N‐phosphanylformamidine 5 (“phosfam”). Alkyl(di‐tert‐butylphosphanyl)amines reacted with Alder's dimer in a 2:1 molar ratio to give N‐phosphanylformamidinium salts; the second equivalent of (alkylamino)phosphane acts as a base. (Arylamino)phosphanes reacted with Alder's dimer to give benzazaphospholium derivatives. To direct the electrophilic attack of Alder's dimer at the nitrogen atom, phosphinoselenoic amides were used. They reacted with Alder's dimer at the selenium atom followed by a selenium–phosphorus shift to give N‐(di‐tert‐butylphosphoroselenoyl)formamidinium salts. The phosphinoselenoic amides with bulky substituents (adamantyl, tBu) underwent cleavage of the N–alkyl bond to afford phosfams. Various key intermediates such as 3 and 22b were isolated and characterized. A convenient method for the synthesis of carbene precursor PIII and PV N‐substituted formamidinium salts was developed.
Theoretical Study of Thorium and Uranium Tetracarbide Molecules
Authors: Pogány Peter , Kovács Attila , Konings Rudy J. M.
Published: January 2014

The electronic structure and ground‐state molecular properties of neutral Th and U tetracarbides were investigated by relativistic multireference calculations using complete active space self‐consistent field/multiconfiguration second‐order perturbation theory (CASSCF/CASPT2) with an all‐electron basis set as well as by density functional theory (B3LYP) in conjunction with relativistic pseudopotentials. The former calculations were extended with complete active space state interaction (CASSI) calculations accounting for spin–orbit coupling. The four carbon atoms can be arranged in various forms around the actinide atom to result in ten structural isomers found altogether in our study. The electronic ground state in both molecules corresponds to a planar fan‐type structure of C2v symmetry, in which the actinide atom is connected to a bent C4 moiety. Three structures arise from various arrangements of C2 moieties around the Th and U, whereas six isomers contain a C3 moiety and a lone C bonded to the actinide. The latter CAnC3‐type structures are very high‐energy structures (over 200 kJ mol–1 with respect to the ground state). The bonding characteristics in the most relevant structures were analysed on the basis of the valence molecular orbitals and the natural bond orbital method. We evaluated and interpreted the vibrational and electronic spectra. The present computed data for UC4 suggest a revision of the assignment of a previously observed IR absorption band to a different isomer.
A Catalyst with Two‐Coordinate Nickel: Theoretical and Catalytic Studies
Authors: Mondal Kartik Chandra , Samuel Prinson P. , Li Yan , Roesky Herbert W. , Roy Sudipta , Ackermann Lutz , Sidhu Navdeep S. , Sheldrick George M. , Carl Elena , Demeshko Serhiy , De Susmita , Parameswaran Pattiyil , Ungur Liviu , Chibotaru Liviu F. , Andrada Diego M.
Published: January 2014

The bisadduct (cAAC)2NiIICl2 [1; cAAC = cyclic (alkyl)(amino)carbene] was directly synthesized by treating cAAC with NiCl2. Compound 1 was reduced to (cAAC)2Ni0 (2) by using lithium diisopropylamide or KC8. Crystals of 2 were stable under an inert gas for several months and decomposed upon heating above 165 °C. On the basis of the calculated natural bond orbital charge values of the nickel atom in 2, the oxidation state of nickel was determined to be between NiI and Ni0 (+0.34). Theoretical calculations suggested a closed‐shell singlet electronic configuration of 2 with little biradical character. Ab initio multiconfigurational C(R)ASSCF/CASPT2 calculations predicted a closed‐shell singlet electronic configuration (Ni0), whereas excited spin states possessed NiI character with unpaired electrons on neighboring carbon atoms. The catalytic activity of complex 2 was investigated for the homocoupling of various unactivated aryl chlorides/fluorides. The biaryls were obtained in good yields at moderate temperature. Theoretical studies showed that an intermediate containing NiIII was more favored than one with NiIV.
A Convergent Strategy for the Synthesis of Second‐Generation Iminosugar Clusters Using “Clickable” Trivalent Dendrons
Authors: Joosten Antoine , Schneider Jérémy P. , Lepage Mathieu L. , Tarnus Céline , Bodlenner Anne , Compain Philippe
Published: January 2014

A convergent strategy to access high‐valency iminosugar clusters based on two successive CuI‐catalysed azide–alkyne cycloadditions is reported. The key step of this approach relies on the grafting of azide‐armed trivalent iminosugar dendrons onto polyalkyne “clickable” scaffolds, thus tripling their initial valency. As a proof of concept, the synthesis of cyclodextrin‐based clusters containing the highest number of peripheral iminosugar ligands reported to date has been achieved. Evaluation of these compounds as mannosidase inhibitors revealed one of the strongest multivalent effects observed so far in glycosidase inhibition.