Efficient Copper-Catalyzed Highly Stereoselective Synthesis of Unprotected C-Acyl Manno-, Rhamno- and Lyxopyranosides

Due to their high stability towards enzymatic hydrolysis C-acyl glycosidic compounds are useful synthetic intermediates for potential candidates in drug discovery. Syntheses for C-acyl mannosides have remained scarce and usually employ donors obtained from lengthy syntheses. Furthermore, syntheses of unprotected C-acyl mannosides have not been reported so far, due to the incapability of the C-acyl mannoside motif with deprotection conditions for protective groups commonly used in carbohydrate chemistry. Herein, we report an efficient and highly α-selective four-step one-pot method for the synthesis of C-acyl α-d -manno-, l -rhamno- and d -lyxopyranosides from easily accessible persilylated monosaccharides and dithianes requiring only trace amounts of a copper source as catalyst and explain the crucial role of the catalyst by mechanistic studies. Furthermore, the C-acyl α-glycosides were easily isomerized to give rapid access to their β-anomers.     

Gradient of the ZAPT2 energy

 An explicit expression for the analytical first derivative of the Z-averaged perturbation theory taken to second order energy, due to Lee and Jayatilaka, is presented for application to high-spin systems described by a restricted open-shell Hartree–Fock wavefunction. The use of frozen core orbitals is incorporated into the derivation. Received: 23 April 2001 / Accepted: 31 August 2001 / Published online: 9 January 2002     

The s-p bonded representatives of the prominent BaAl4 structure type: a case study on structural stability of polar intermetallic network structures

This work presents a detailed, combined experimental and theoretical study on the structural stability of s-p bonded compounds with the BaAl4 structure type (space group I4/mmm, Z = 2) as part of a broad program to investigate the complex questions of structure formation and atomic arrangements in polar intermetallics. From ab initio calculations employing pseudopotentials and a plane wave basis set, we extracted optimized structural parameters, binding energies, and the electronic structure of the systems AeX(III)4, AeX(II)2X(IV)2, AeX(II)2X(III)2 (Ae = Ca, Sr, Ba; X(II) = Mg, Zn; X(III) = Al, Ga; X(IV) = Si, Ge). For all systems we found a pronounced pseudo-gap in the density of states separating network X42- bonding from antibonding electronic states that coincides with the Fermi level for an electron count of 14 electrons per formula unit, the optimum value for stable BaAl4-type polar intermetallics. However, the synthesis and structural characterization (from X-ray single crystal and powder diffraction data) of the new compounds AeZn2-Al2+, AeZn2-deltaGa2+delta (Ae = Ca, Sr, Ba; delta = 0-0.2) and AeMg0.9Al3.1, AeMg1.7Ga2.3 (Ae = Sr, Ba) manifested that electron deficiency is rather frequent for BaAl4-type polar intermetallics. The site preference for different "X" elements in the ternary systems was quantified by calculating "coloring energies", which, for some systems, was strongly dependent on the size of the electropositive Ae component. The Ae2+ cations decisively influence the nearest neighbor distances in the encapsulating polyanionic networks X4(2-) and the structures of these networks are surprisingly flexible to the size of the Ae component without changing the overall bonding picture. A monoclinically distorted variant of the BaAl4 structure occurs when the cations become too small for matching the size of encapsulating X4(2-) cages. An even larger size mismatch leads to the formation of the EuIn4 structure type.     

Determination of total dietary fiber in selected foods containing resistant maltodextrin by enzymatic-gravimetric method and liquid chromatography: collaborative study

A method was developed for determination of total dietary fiber (TDF) in foods containing resistant maltodextrin (RMD) which includes nondigestible carbohydrates that are not fully recovered as dietary fiber by conventional TDF methods such as AOAC 985.29 or 991.43. Because the average molecular weight (MW) of RMD is 2000 daltons, lower MW soluble dietary fiber components do not precipitate in 78% ethanol; therefore, RMD is not completely quantitated as dietary fiber by current AOAC methods. The accuracy and precision of the method was evaluated through an AOAC collaborative study. Ten laboratories participated and assayed 12 test portions (6 blind duplicates) containing RMD. The 6 test pairs ranged from 1.5 to 100% RMD. The method consisted of the following steps: (1) The insoluble dietary fiber (IDF) and high MW soluble dietary fiber (HMWSDF) were determined by AOAC 985.29. (2) Ion exchange resins were used to remove salts and proteins contained in the AOAC 985.29 filtrates (including ethanol and acetone). (3) The amount of low MWRMD (LMWRMD) in the filtrates were determined by liquid chromatography. (4) The TDF was calculated by summation of the IDF, HMWSDF, and LMWRMD fractions having nondigestible carbohydrates with a degree of polymerization of 3 and higher. Repeatability standard deviations (RSDr) were 1.33-7.46%, calculated by including outliers, and 1.33-6.10%, calculated by not including outliers. Reproducibility standard deviations (RSDR) were 2.48-9.39%, calculated by including outliers, and 1.79-9.39%, calculated by not including outliers. This method is recommended for adoption as Official First Action.     

Multiple Li positions inside oxygen octahedra in lithiated TiO2 anatase

Intercalation of Li in TiO2 anatase results in a phase separation in a Li-poor and a Li-rich phase. The local lithium configuration in the coexisting crystallographic phases is resolved by detailed analysis of neutron diffraction data. In each of the phases, two distinct positions within the octahedral interstices are found, with a temperature-dependent occupancy. A combination of quasi-elastic neutron scattering and force field molecular dynamics simulations shows that Li is hopping on a picosecond time scale between the two sites in the octahedral interstices. The results also suggest a specific Li arrangement along the crystallographic a direction, albeit without long range order. It is likely that multiple discrete Li sites within a distorted oxygen octahedron occur not only in intercalated TiO2 anatase but also in other (transition metal) oxides.     

Dynamics of a triphenylene discotic molecule,HAT6, in the columnar and isotropic liquid phases

Discotic molecules have planar, disklike polyaromatic cores that can self-assemble into "molecular wires". Highly anisotropic charge transfer along the wires arises when there is sufficient intermolecular overlap of the pi-orbitals of the molecular cores. Discotic materials can be applied in molecular electronics, field-effect transistors, and-recently with record quantum efficiencies-photovoltaics (Schmidt-Mende, L.; Fechtenk?tter, A.; Müllen, K.; Moons, E.; Frien, R. H.; MacKenzie, J. D. Science 2001, 293, 1119). A combination of quasielastic neutron scattering (QENS) measurements with molecular dynamics simulations on the discotic molecule hexakis(n-hexyloxy)triphenylene (HAT6) shows that the dynamics of the cores and tails of discotic molecules are strongly correlated. Core and tail dynamics are not separated, the system being characterized by overall in-plane motion, on a time scale of 0.2 ps, and softer out-of-plane motions at 7 ps. Because charge transfer between the molecules is on similar time scales, these motions are relevant for the conducting properties of the materials. Both types of motion are dominated by van der Waals interactions. Small-amplitude in-plane motions in which the disks move over each other are almost entirely determined by tail/tail interactions, these also playing an important role in the out-of-plane motion. The QENS measurements reveal that these motions are little changed by passing from the columnar phase to the isotropic liquid phase, just above the clearing temperature. The model of four HAT6 molecules in a column reproduces the measured QENS spectrum of the liquid phase, suggesting that correlations persist within the liquid phase over about this number of disks.     

Metal Olefin Complexes: Revisiting the Dewar−Chatt−Duncanson Model and Deriving Reactivity Patterns from Carbon‐13 NMR Chemical Shift

Metal olefin complexes that are ubiquitous intermediates in catalysis are investigated by a detailed analysis of their ¹³C‐NMR chemical shift tensors. This analysis allows evidencing specific electronic features, namely the olefin‐to‐metal σ‐donation and the metal‐to‐olefin π‐backdonation as proposed in the Dewar?Chatt?Duncanson model. Apart from these interactions, the chemical shift tensor analysis reveals an additional ligand‐to‐metal π‐donation of the olefin σ(C=C) orbital in systems with suitably oriented vacant d‐orbitals. This interaction which is not accounted for in the Dewar?Chatt?Duncanson model explains the reactivity of this type of metal olefin complexes towards oxidative cyclization (olefin insertion) and protonolysis.     

Synthesis of water-soluble fullerene-containing vinyl polymers by low-temperature radiation-induced living polymerization

Water-soluble polymers of acrylamide and acrylic acid that contain fullerene (more than 90% C₆₀) have been prepared by the low-temperature radiation-induced living polymerization. In the absorption spectra of these polymers, a monotonically decaying absorption typical of the covalently bound fullerene or its associates is observed in the range 240–700 nm. The radiation initiation of the process allows preparation of high-purity polymers useful for designing medicinal preparations.