Chiral Interlocked Corrole Dimers Directly Linked at Inner Carbon Atoms of Confused Pyrrole Rings

A facile synthetic strategy towards conformationally stable chiral chromophores based on dimeric porphyrinoids has been established. A peculiar class of face-to-face intramolecularly interlocked corrole dimers were formed by the oxidative C−C coupling linked at the inner carbon sites upon simple treatment of copper(II) ions. Their intrinsic electronic structures were modulated by the peripheral corrole ring annulations, which lead to distinct optical properties and redox profiles. The stereogenic carbon centers implemented in the confused corrole skeleton provided a rationale for designing novel chiral materials.     

Stereoselective synthesis of trisubstituted alkenylboranes by palladium-catalysed reaction of alkynyltriarylborates with aryl halides

The palladium-catalysed reaction of alkynyltriarylborates with aryl halides afforded trisubstituted alkenylboranes, in which two different aryl groups were installed across the carbon-carbon double bond in a cis arrangement.     

Thin-layer chromatographic behavior of rare earths on silica gel with aqueous alkaline earth metal nitrate solutions as mobile phases

The TLC behavior of all the rare earths except Pm has been surveyed on silica gel (pH 7.0) pretreated with 0.1 mol L(-1) tris(hydroxymethyl)aminomethane and 0.1 mol L(-1) HCl with aqueous nitrate solutions of alkaline earth metals as mobile phases. The RF values of the lanthanides varied in a regular and characteristic way accompanied by the tetrad effect with increasing atomic number, and when the mobile phases were changed the RF values of each metal decreased in the order Mg2+ > Ca2+ > Sr2+ > Ba2+, as the crystal ionic radii of the alkaline earth metals increased. This adsorption sequence was not observed with alkali metal nitrate and alkali metal chloride mobile phases. A brief discussion concerning the effect on RF values of the solvent cations and the adsorption mechanism is included; also presented are typical chromatograms for the separation of multi-component mixtures containing adjacent lanthanides.     

Synthetic Studies on Sialoglycoconjugates 60: α-Stereocontrolled,Glycoside Synthesis of Trimeric Sialic Acid with Galactose and Lactose Derivatives

Abstract

α-Stereocontrolled, glycoside synthesis of trimeric sialic acid is described toward a systematic approach to the synthesis of sialoglycoconjugates containing an α-sialyl-(2→8)-α-sialyl-(2→8)-sialic acid unit α-glycosidically linked to O-3 of a galactose residue in their oligosaccharide chains. Glycosylation of 2-(trimethylsilyl)ethyl 6-O-benzoyl-β-d-galactopyranoside (4) or 2-(trimethylsilyl)ethyl 2,3,6,2′,6′-penta-O-benzyl-β-lactoside (5), with methyl [phenyl 5-acetamido-8-O-[5-acetamido-8-O-(5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-d-glycero-α-d-galacto-2-nonulopyranosylono-1”, 9′-lactone)-4,7-di-O-acetyl-3,5-dideoxy-d-glycero-α-d-galacto-2-nonulopyranosylono-1′, 9-lactone]-4,7-di-O-acetyl-3,5-dideoxy-2-thio-d-glycero-d-galacto-2-nonulopyranosid]onate (3), using N-iodosuccinimide-trifluoromethanesulfonic acid as a promoter, gave the corresponding α-glycosides 6 and 8, respectively. The glycosyl donor 3 was prepared from trimeric sialic acid by treatment with Amberlite IR-120 (H⁺) resin in methanol, O-acetylation, and subsequent replacement of the anomeric acetoxy group with phenylthio. Compounds 6 and 8 were converted into the per-O-acyl derivatives 7 and 9, respectively.     

Forced proximity of nitroxide groups in pincer compounds with a xanthene spacer

We designed bisnitroxide compounds where the radical sites are located close to each other in a molecule. Two new pincer-type bisnitroxide compounds have been synthesized, involving xanthene-4,5-diyl as a spacer and tert-butyl phenyl nitroxides as arms. From the X-ray crystal structure analysis, the shortest intramolecular interatomic N?O and O?O distances respectively are 5.074(6) and 5.258(6) Å for the m,m′-derivative and 3.624(3) and 3.771(3) Å for the p,p′-derivative. The N?O distance in the latter satisfies the empirical criterion for possible dimerization/degradation reaction accompanied by dia-/paramagnetic transition. However, the magnetic study clarified paramagnetic behavior in all the temperature range. According to a singlet-triplet model, antiferromagnetic couplings were characterized with 2J/k_B = ?7.71(2) and ?8.83(4) K for the m,m′ and p,p′-derivatives, respectively. The present result suggests that a more flexible spacer is required for realization of possible dia-/paramagnetic transition.     

The first halogen-substituted cyclotrigermenes: a unique halogen walk over the three-membered ring skeleton and facial stereoselectivity in the Diels-Alder reaction

Dark red crystals of the halogen-substituted cyclotrigermenes [(tBu3Si)3Ge3X; X = Cl, Br, I] were obtained in good yields by the reaction of [(tBu3Si)3Ge3]+.TTFPB- (TTFPB- = tetrakis(2,3,5,6-tetrafluorophenyl)borate) with potassium halides (KCl, KBr, or KI) in diethyl ether. The crystal structures of the halogen-substituted cyclotrigermenes reveal a cis-bent Ge=Ge double bond, caused by the introduction of the electronegative halogen atom on the sp3 germanium atom of cyclotrigermene. In solution, an intramolecular halogen migration over the three-membered ring skeleton was observed. Facial stereoselectivity in the Diels-Alder reaction of new cyclotrigermenes with 2,3-dimethyl-1,3-butadiene is also reported.     

Skew-symmetric form of convective terms and fully conservative finite difference schemes for variable density low-Mach number flows

The form of convective terms for compressible flow equations is discussed in the same way as for an incompressible one by Morinishi et al. [Y. Morinishi, T.S. Lund, O.V. Vasilyev, P. Moin, Fully conservative higher order finite difference schemes for incompressible flow, J. Comput. Phys. 124 (1998) 90], and fully conservative finite difference schemes suitable for shock-free unsteady compressible flow simulations are proposed. Commutable divergence, advective, and skew-symmetric forms of convective terms are defined by including the temporal derivative term for compressible flow. These forms are analytically equivalent if the continuity is satisfied, and the skew-symmetric form is secondary conservative without the aid of the continuity, while the divergence form is primary conservative. The relations between the present and existing quasi-skew-symmetric forms are also revealed. Commutable fully discrete finite difference schemes of convection are then derived in a staggered grid system, and they are fully conservative provided that the corresponding discrete continuity is satisfied. In addition, a semi-discrete convection scheme suitable for compact finite difference is presented based on the skew-symmetric form. The conservation properties of the present schemes are demonstrated numerically in a three-dimensional periodic inviscid flow. The proposed fully discrete fully conservative second-order accurate scheme is also used to perform the DNS of compressible isotropic turbulence and the simulation of open cavity flow.     

Quantum phase transitions to charge-ordered and Wigner-crystal states under the interplay of lattice commensurability and long-range Coulomb interactions

The relationship among the Wigner crystal, charge ordering, and the Mott insulator is studied by the path-integral renormalization group method in two-dimensional systems with long-range Coulomb interaction. In contrast to the insensitivity of the Hartree-Fock results, the stability of the solid drastically decreases with the decrease in the lattice commensurability. The transition to liquid occurs at the electron gas parameter r(s) approximately 2 for the filling n=1/2, showing a large reduction from r(s) approximately 35 in the continuum limit. A correct account of quantum fluctuations is crucial to understanding the charge-order stability generally observed only at simple fractional fillings and the nature of quantum liquids away from them.     

Spin-triplet superconductivity in UNi(2)Al(3) revealed by the (27)Al Knight shift measurement

We report (27)Al Knight shift ( (27)K) measurement on a single-crystal UNi(2)Al(3) that reveals a coexistence of superconductivity and a spin-density-wave (SDW) type of magnetic ordering ( T(SDW) = 4.5 K). The spin part of (27)K, (27)K(s), does not change down to 50 mK across the superconducting (SC) transition temperature T(c) approximately 0.9 K. In contrast with the isostructural compound UPd(2)Al(3) ( T(c) approximately 2 K), which was identified to be a spin-singlet d-wave superconductor, the behavior of (27)K strongly supports that UNi(2)Al(3) , like UPt(3) and Sr(2)RuO(4), belongs to a class of spin-triplet SC pairing state superconductors.