Hydrosilanes are not always a reducing reagent: a ruthenium-catalyzed introduction of primary alkyl groups to electron-rich aromatic rings using esters as a source of the alkyl groups

A triruthenium cluster, (μ₃, η², η³, η⁵-acenaphthylene)Ru₃(CO)₇ effectively catalyzes primary-alkylation reaction of electron-rich aromatic rings using a combination of hydrosilane and ester as a source of the primary-alkyl group. The reaction involves electrophilic substitution of arenes by carbocationic species stabilized by a neighboring alkoxy or siloxy group generated during the reduction of esters giving alkylated arenes after reductive removal of the alkoxy or siloxy group at the benzylic position.     

New approach to oligotriazoles using a cobalt complex of propargyl azides as a synthetic component

We have developed an efficient method for preparation of triazolamers using a dicobalt hexacarbonyl complex of propargyl azides (CPA) as a synthetic component. Several types of CPAs possessing the side chains found in the natural amino acids were prepared by Nicholas reaction as well as by a reaction of propargyl azides with dicobalt octacarbonyl. Triazolamers with both amino and carboxyl termini were readily synthesized by repetitive reaction sequence involving a copper-catalyzed 1,3-dipolar cycloaddition followed by an oxidative deprotection.     

Stacked 1,3,5-tris[(2,5-dimethylphenyl)ethynyl]benzenes: dimer and conjugated microporous polymer

A new [2.2]paracyclophane compound consisting of two 1,3,5-tris[(2,5-dimethylphenyl)ethynyl]benzenes stacked in proximity to each other. The compound exhibited a unique absorption band (cyclophane band) and an emission from the phane state, both of which were derived from the π-π stacking of the poorly extended conjugation systems of 1,3,5-tris[(2,5-dimethylphenyl)ethynyl]benzene. In addition, a conjugated microporous polymer (CMP) that comprises pseudo-para-substituted [2.2]paracyclophane was prepared. The obtained CMP is regarded as a polymer, in which 1,3,5-tris[(2,5-dimethylphenyl)ethynyl]benzenes are infinitely stacked to form a network structure. The CMP exhibited a type I nitrogen gas sorption profile and an H4-like hysteresis loop, and possessed the slit-like mesopores with a BET surface area of 501 m² g⁻¹.     

Mapping of the primary mannose binding site of pradimicin A

Pradimicin A (PRM-A) is an actinomycete-derived antibiotic with the lectin-like property of being able to recognize D-mannopyranoside (Man) in the presence of Ca(2+) ion. PRM-A and its derivatives have been attracting a great deal of attention as the only family of natural carbohydrate receptors with nonpeptidic skeleton and, more recently, as conceptually novel drug candidates for human immunodeficiency virus (HIV). Despite its scientific interest and potential therapeutic importance, understanding how PRM-A recognizes Man has been severely limited. Conventional interaction analysis of PRM-A with Man in solution has been frustrated by aggregation of PRM-A and the three-component equilibrium consisting of the [PRM-A(2)/Ca(2+)], [PRM-A(2)/Ca(2+)/Man(2)], [PRM-A(2)/Ca(2+)/Man(4)] complexes, and their mixed oligomers. In this Article, we demonstrate the interaction analysis of PRM-A with methyl α-D-mannopyranoside (Man-OMe) in the solid state, which benefits from aggregate-forming propensity of PRM-A and eliminates the problem associated with the complicated equilibrium in solution. Isothermal titration calorimetry (ITC) analysis and coprecipitation experiments revealed that the primary Man binding of PRM-A is markedly tighter than the secondary one, leading to preparation of the solid aggregate solely composed of the [PRM-A(2)/Ca(2+)/Man-OMe(2)] complex. The simple 1:1 complexes of biosynthetically (13)C-enriched PRM-As and [(13)C(6)]Man-OMe facilitated the analysis of the primary Man binding of PRM-A by two-dimensional dipolar-assisted rotational resonance (2D-DARR), which clearly identified that the cavity consisted of D-alanine moiety and ABC rings of PRM-A is the Man binding site. Interestingly, the proposed Man binding site of PRM-A seems to resemble the typical architecture of artificial carbohydrate receptors.     

Confinement in carbon nanospace-induced production of KI nanocrystals of high-pressure phase

An outstanding compression function for materials preparation exhibited by nanospaces of single-walled carbon nanohorns (SWCNHs) was studied using the B1-to-B2 solid phase transition of KI crystals at 1.9 GPa. High-resolution transmission electron microscopy and synchrotron X-ray diffraction examinations provided evidence that KI nanocrystals doped in the nanotube spaces of SWCNHs at pressures below 0.1 MPa had the super-high-pressure B2 phase structure, which is induced at pressures above 1.9 GPa in bulk KI crystals. This finding of the supercompression function of the carbon nanotubular spaces can lead to the development of a new compression-free route to precious materials whose syntheses require the application of high pressure.     

Allylic substitution on cyclopentene and -hexene rings with alkynylcopper reagents

Substitution of cyclic allylic picolinates with a reagent derived from TMS-C≡CMgBr and a copper salt was investigated. Although the previous type of reagent (TMSC≡CMgBr and CuBr·Me(2)S) developed for linear allylic picolinates was less product selective and regioselective, the Cu(acac)(2)-derived reagent was highly selective (94-95%) to afford the S(N)2' product in good yields. As an application, several C-C bond formations at the acetylenic carbon and the synthesis of the PG intermediate were studied with success.     

Asymptotic stability for quasi-linear systems whose linear approximation is not assumed to be uniformly attractive

Sufficient conditions are obtained for uniform stability and asymptotic stability of the zero solution of two-dimensional quasi-linear systems under the assumption that the zero solution of linear approximation is not always uniformly attractive. A class of quasi-linear systems considered in this paper includes a planar system equivalent to the damped pendulum x′??+ h(t)x??+ sin x = 0, where h(t) is permitted to change sign. Some suitable examples are included to illustrate the main results.     

Direct observation of lithium staging in partially delithiated LiFePO4 at atomic resolution

Lithium ions in LiFePO(4) were observed directly at atomic resolution by an aberration-corrected annular-bright-field scanning transmission electron microscopy technique. In addition, it was found in partially delithiated LiFePO(4) that the remaining lithium ions preferably occupy every second layer, along the b axis, analogously to the staging phenomenon observed in some layered intercalation compounds. This new finding challenges previously proposed LiFePO(4)/FePO(4) two-phase separation mechanisms.     

Structural study of a series of layered rare-earth hydroxide sulfates

We report structure analysis of a new family of rare-earth hydroxides Ln(2)(OH)(4)SO(4)·2H(2)O (Ln = Pr, Nd, Sm, Eu, Gd, Tb) from synchrotron X-ray and electron diffraction data. Rietveld profile analysis revealed that all members were isostructural and crystallized in a face-centered monoclinic system A2/m (No. 12), in which the monoclinic angles were approximately equal to the right angle, varying from 90.387(1)° for Pr sample to 90.0718(3)° for Tb sample. The structure consisted of LnO(9) polyhedra connected by μ(3)-hydroxyl groups and μ(2)-water molecules, forming a corrugated two-dimensional layer, which was pillared by bidentated sulfate ions. This series of compounds had a supercell a' = 2a, b' = 2b because of the local orientation ordering of SO(4)(2-). Structural features along the series, such as unit-cell parameters and average Ln-O distances, represented a progressive contraction associated with the shrinking radius of the lanthanide cations from Pr to Tb.     

Photoinduced Ordering Transition in Microdroplets of Liquid Crystals with Azo‐Dendrimer

Ordering transitions are observed in azo‐dendrimer‐dissolved nematic liquid crystal (NLC) droplets dispersed in a glycerol matrix. The dendrimer molecules are spontaneously attached at the interface between NLC and glycerol, so that the nematic directors orient perpendicular to the interface, in the radial configuration. Photoisomerization makes the directors be tangential to the interface, in a photoinduced ordering transition from radial to bipolar structure. Similar experiments are conducted both in cholesteric (Ch) and smectic‐A (SmA) LC droplets. Complicated photoinduced ordering transitions are also observed in Ch and SmA droplets, and the associated molecular orientation changes are discussed. Photoisomerizable azo‐dendrimer molecules provide a possible way to control orientation, even in microdroplet systems in which the interface cannot be treated by conventional surface agents.