Mesoporous Silica MCM‐41 Supported N‐Heterocyclic Carbene‐Pd Complex for Heck and Sonogashira Coupling Reactions

Heterocyclic carbene‐Pd complex was anchored onto the mesoporous silica MCM‐41 which exhibits high catalytic activity in Heck reaction under phosphine free reaction conditions for the reaction of iodo/bromoarenes with olefinic compounds such as butyl acrylate, isopropyl acrylate and styrene. This catalytic system also showed high activity for Sonogashira coupling reaction of various aryl halides under copper, phosphine and solvent‐free reaction conditions. The air and thermally stable catalyst were reused several times without significant loss of its activity. High efficiency of the catalyst along with its recycling ability and the rather low Pd‐loading demonstrated in both Heck and Sonogashira coupling reactions are the merits of the presented catalyst system.     

Alcohol oxidation reactions catalyzed by ruthenium–carbonyl complexes of thioarylazoimidazoles

Alcohols are oxidized by N‐methylmorpholine‐N‐oxide (NMO), Bu^tOOH and H₂O₂ to the corresponding aldehydes or ketones in the presence of catalyst, [RuH(CO)(PPh₃)₂(SRaaiNR′)]PF₆ ( 2 ) and [RuCl(CO)(PPh₃)(S_κRaaiNR′)]PF₆ ( 3 ) (SRaaiNR′ ( 1 ) = 1‐alkyl‐2‐{(o‐thioalkyl)phenylazo}imidazole, a bidentate N(imidazolyl) (N), N(azo) (N′) chelator and S_κRaaiNR′ is a tridentate N(imidazolyl) (N), N(azo) (N′), S_κ‐R is tridentate chelator; R and R′ are Me and Et). The single‐crystal X‐ray structures of [RuH(CO)(PPh₃)₂(SMeaaiNMe)]PF₆ ( 2a ) (SMeaaiNMe = 1‐methyl‐2‐{(o‐thioethyl)phenylazo}imidazole) and [RuH(CO)(PPh₃)₂(SEtaaiNEt)]PF₆ ( 2b ) (SEtaaiNEt = 1‐ethyl‐2‐{(o‐thioethyl)phenylazo}imidazole) show bidentate N,N′ chelation, while in [RuCl(CO)(PPh₃)(S_κEtaaiNEt)]PF₆ ( 3b ) the ligand S_κEtaaiNEt serves as tridentate N,N′,S chelator. The cyclic voltammogram shows Ru^III/Ru^II (~1.1 V) and Ru^IV/Ru^III (~1.7 V) couples of the complexes 2 while Ru^III/Ru^II (1.26 V) couple is observed only in 3 along with azo reductions in the potential window +2.0 to ?2.0 V. DFT computation has been used to explain the spectra and redox properties of the complexes. In the oxidation reaction NMO acts as best oxidant and [RuCl(CO)(PPh₃)(S_κRaaiNR′)](PF₆) ( 3 ) is the best catalyst. The formation of high‐valent Ru^IV=O species as a catalytic intermediate is proposed for the oxidation process. Copyright © 2014 John Wiley & Sons, Ltd.     

Peptide Conjugates of a Nonsteroidal Anti‐Inflammatory Drug as Supramolecular Gelators: Synthesis,Characterization, and Biological Studies

Indomethacin ( IND ), which is a well‐known nonsteroidal anti‐inflammatory drug (NSAID), was conjugated with various naturally occurring amino acids. Most of these bioconjugates were capable of gelling pure water, a solution of NaCl (0.9 wt %), and phosphate‐buffered saline (pH 7.4), as well as a few organic solvents. The gels were characterized by table‐top and dynamic rheology, and electron microscopy. Variable‐temperature ¹H NMR spectroscopy studies on a selected gel were performed to gain insights into the self‐assembly process during gel formation. Both 1D and 2D hydrogen‐bonded networks were observed in the single‐crystal structures of two of the gelators. Plausible biological applications of the hydrogelators were evaluated with the ultimate aim of drug delivery in a self‐delivery fashion. All hydrogelators were stable in phosphate‐buffered saline at pH 7.4 at 37 °C, and biocompatible in mouse macrophage RAW 264.7 cell line (3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide assay). Two of the most biocompatible hydrogelators displayed an anti‐inflammatory response comparable to that of the parent drug IND in prostaglandin E₂ assay. Release of the bioconjugates into the bulk solvent interfaced with the corresponding hydrogels indicated their plausible future application in drug delivery.     

Three‐dimensional networks containing rectangular Sr4 and Ba4 units: Synthesis,structure, bonding,and potential application for Ne gas separation

New porous three‐dimensional metal‐organic frameworks are synthesized that contain infinite chains of Sr_n and Ba_n rectangles. Their structures are elucidated by means of spectroscopic techniques such as nuclear magnetic resonance and Fourier transform infrared, and the respective crystal structures are determined. The electronic structure of basic units of the crystals are computed using density functional theory at the B3LYP/6‐31G(d,p)/def2‐TZVP level, and the bonding and reactivity are analyzed using natural bond orbital analysis, the quantum theory of atoms in molecules, and conceptual density functional theory. The possibilities of noble gas (Ng) storage inside the crystal structures are explored through modeling a Ng atom inside the frozen geometry of the crystal. It was found that a neon atom can fit into a cavity in the Sr and Ba crystal structures whereas other Ngs (He, Ar, Kr) exhibit repulsive interactions with the crystal structure. Ab initio molecular dynamics simulations for up to 500 fs at 77 and 298 K suggest that the structures incorporating a neon atom are kinetically stable. © 2015 Wiley Periodicals, Inc.     

Ruthenium(II)‐Catalyzed CH Activation with Isocyanates: A Versatile Route to Phthalimides

A cationic ruthenium(II)‐complex was utilized in the efficient synthesis of phthalimide derivatives by C?H activation with synthetically useful amides. The reaction proceeded through a mechanistically unique insertion of a cycloruthenated species into a C?Het multiple bond of isocyanate. The novel method also proved applicable for the synthesis of heteroaromatic unsymmetric diamides as well as a potent COX‐2 enzyme inhibitor.     

Ultrafast FRET to Study Spontaneous Micelle‐to‐Vesicle Transitions in an Aqueous Mixed Surface‐Active Ionic‐Liquid System

The spontaneous micelle‐to‐vesicle transition in an aqueous mixture of two surface‐active ionic liquids (SAILs), namely, 1‐butyl‐3‐methylimidazolium n‐octylsulfate ([C₄mim][C₈SO₄]) and 1‐dodecyl‐3‐methylimidazoium chloride ([C₁₂mim]Cl) is described. In addition to detailed structural characterization obtained by using dynamic light scattering, transmission electron microscopy (TEM), and cryogenic TEM techniques, ultrafast fluorescence resonance energy transfer (FRET) from coumarin 153 (C153) as a donor (D) to rhodamine 6G (R6G) as an acceptor (A) is also used to study micelle–vesicle transitions in the present system. Structural transitions of SAIL micelles ([C₄mim][C₈SO₄] or [C₁₂mim]Cl micelles) to mixed SAIL vesicles resulted in significantly increased D –A distances, and therefore, increased timescale of FRET. In [C₄mim][C₈SO₄] micelles, FRET between C153 and R6G occurs on an ultrafast timescale of 3.3 ps, which corresponds to a D –A distance of about 15 Å. As [C₄mim][C₈SO₄] micelles are transformed into mixed micelles upon the addition of a 0.25 molar fraction of [C₁₂mim]Cl, the timescale of FRET increases to 300 ps, which suggests an increase in the D –A distance to 31 Å. At a 0.5 molar fraction of [C₁₂mim]Cl, unilamellar vesicles are formed in which FRET occurs on multiple timescales of about 250 and 2100 ps, which correspond to D –A distances of 33 and 47 Å. Although in micelles and mixed micelles the obtained D –A distances are well correlated with their radius, in vesicles the obtained D –A distance is within the range of the bilayer thickness.     

Coexistence of 3d‐Ferromagnetism and Superconductivity in [(Li1−xFex)OH](Fe1−yLiy)Se

Superconducting [(Li_1?xFe_x)OH](Fe_1?yLi_y)Se (x≈0.2, y≈0.08) was synthesized by hydrothermal methods and characterized by single‐crystal and powder X‐ray diffraction. The structure contains alternating layers of anti‐PbO type (Fe_1?yLi_y)Se and (Li_1?xFe_x)OH. Electrical resistivity and magnetic susceptibility measurements reveal superconductivity at 43 K. An anomaly in the diamagnetic shielding indicates ferromagnetic ordering near 10 K while superconductivity is retained. The ferromagnetism is from the iron atoms in the (Li_1?xFe_x)OH layer. Isothermal magnetization measurements confirm the superposition of ferromagnetic and superconducting hysteresis. The internal ferromagnetic field is larger than the lower, but smaller than the upper critical field of the superconductor. The formation of a spontaneous vortex phase where both orders coexist is supported by ⁵⁷Fe‐Mössbauer spectra, ⁷Li‐NMR spectra, and μSR experiments.     

Hydrated ferric sulfate catalyzed synthesis of 5,6-unsubstituted 1,4-dihydropyridines using three-component reaction

A wide variety of 5,6-unsubstituted 1,4-dihydropyridines derivatives (4a–q) were synthesized through a one-pot three-component reaction from α,β-unsaturated aldehydes, amines, and 1,3-diketones at room temperature using hydrated ferric sulfate as a Lewis acid catalyst. The key features of the present protocol are mild and simple reaction procedure, good to excellent yields, and use of inexpensive, recyclable, and environmentally benign catalyst.     

Studying Reaction Intermediates Formed at Graphenic Surfaces

We report in-situ production and detection of intermediates at graphenic surfaces, especially during alcohol oxidation. Alcohol oxidation to acid occurs on graphene oxide-coated paper surface, driven by an electrical potential, in a paper spray mass spectrometry experiment. As paper spray ionization is a fast process and the time scale matches with the reaction time scale, we were able to detect the intermediate, acetal. This is the first observation of acetal formed in surface oxidation. The process is not limited to alcohols and the reaction has been extended to aldehydes, amines, phosphenes, sugars, etc., where reaction products were detected instantaneously. By combining surface reactions with ambient ionization and mass spectrometry, we show that new insights into chemical reactions become feasible. We suggest that several other chemical transformations may be studied this way. This work opens up a new pathway for different industrially and energetically important reactions using different metal catalysts and modified substrate.