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Kawabata T Muramatsu W Nishio T Shibata T Schedel H 《Journal of the American Chemical Society》2007,129(42):12890-12895
An organocatalytic method for the chemo- and regioselective acylation of monosaccharides has been developed. Treatment of octyl beta-D-glucopyranoside with isobutyric anhydride in the presence of 10 mol % of a C2-symmetric chiral 4-pyrrolidinopyridine catalyst (1) at -50 degrees C gave the 4-O-isobutyryl derivative as the sole product in 98% yield. Thus, chemoselective acylation, favoring a secondary hydroxyl group in the presence of a free primary hydroxyl group, and regioselective acylation, favoring one of three secondary hydroxyl groups, took place with perfect selectivity. A competitive acylation between octyl beta-D-glucopyranoside and a primary alcohol (2-phenylethanol) with 1.1 equiv of isobutyric anhydride in the presence of 1 gave the 4-O-isobutyrate of octyl beta-D-glucopyranoside with 99% regioselectivity in 98% yield, which indicates that acylation of the secondary hydroxyl group at C(4) of the carbohydrate proceeds in an accelerative manner. A possible mechanism, involving multiple hydrogen-bonding between 1 and the monosaccharide, is proposed for the chemo- and regioselective acylation. 相似文献
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755.
Kanno O Kuriyama W Wang ZJ Toste FD 《Angewandte Chemie (International ed. in English)》2011,50(42):9919-9922
Alcohol is key: Regio- and enantioselective hydroamination of 1,3-dienes has been achieved with the dinuclear catalyst (R)-DTBM-SEGPHOS. The rate and selectivity of the reaction are enhanced by alcohol additives like menthol, which coordinates the cationic gold(I) to generate a Br?nsted acid that can participate in catalysis. Mbs=p-methoxybenzenesulfonyl. 相似文献
756.
The first-principles studies were performed for the modified graphites with various edge conformations, which revealed that the NH edge facilitates easy transfer of an electron into the adsorbed O(2). 相似文献
757.
Morisue M Suzuki W Kuroda Y 《Dalton transactions (Cambridge, England : 2003)》2011,40(39):10047-10054
A highly congested hexameric subphthalocyanine array was synthesized by axial chlorine-to-phenoxy substitution of a hexakis(4-hydroxyphenyl)benzene based subphthalocyanine, and photoinduced symmetry-breaking charge separation was demonstrated in polar solvent. 相似文献
758.
Wataru Kumagai 《Linear algebra and its applications》2011,434(1):224-231
Classical information geometry has emerged from the study of geometrical aspect of the statistical estimation. Cencov characterized the Fisher metric as a canonical metric on probability simplexes from a statistical point of view, and Campbell extended the characterization of the Fisher metric from probability simplexes to positive cone . In quantum information geometry, quantum states which are represented by positive Hermitian matrices with trace one are regarded as an extension of probability distributions. A quantum version of the Fisher metric is introduced, and is called a monotone metric. Petz characterized the monotone metrics on the space of all quantum states in terms of operator monotone functions. A purpose of the present paper is to extend a characterization of monotone metrics from the space of all states to the space of all positive Hermitian matrices on finite dimensional Hilbert space. This characterization corresponds quantum modification of Campbell’s work. 相似文献
759.
The structural stability of cagelike boron clusters with octahedral and tetrahedral symmetries has been investigated by means of first-principles calculations. Twenty-eight cluster models, ranging from B(10) to B(66), were systematically constructed using regular and semiregular polyhedra as prototypes. The binding energies per atom were, on the whole, slightly lower than those of icosahedral clusters B(80) and B(100), which are supposed to be the most stable in the icosahedral group. The larger clusters did not always have higher binding energies. Isothermal molecular dynamics simulations were performed to determine the deformation temperatures at which clusters began to break or change their structures. We found eight clusters that had nonzero deformation temperatures, indicating that they are in metastable states. The octahedral cluster B(18) had the highest deformation temperature among these, similar to that of icosahedral B(80) and B(100). The analysis of the electronic structure of B(18) showed that it attained this high stability owing to Jahn-Teller distortion. 相似文献
760.
Negishi Y Kurashige W Kamimura U 《Langmuir : the ACS journal of surfaces and colloids》2011,27(20):12289-12292
We report the isolation and structural characterization of an octaneselenolate-protected Au(25) cluster ([Au(25)(SeC(8)H(17))(18)](-)). Isolated [Au(25)(SeC(8)H(17))(18)](-) was characterized by various analytical techniques. The results strongly suggest that [Au(25)(SeC(8)H(17))(18)](-) possesses a similar geometric structure to the well-studied thiolate (RS)-protected Au(25) cluster ([Au(25)(SR)(18)](-)) and that the charge transfer between the metal atoms and ligands in [Au(25)(SeC(8)H(17))(18)](-) is lower than that in [Au(25)(SR)(18)](-). To the best of our knowledge, this is the first report of the isolation of a selenolate-protected gold cluster. [Au(25)(SeC(8)H(17))(18)](-) is an ideal compound for determining how changing the ligand from thiolate to selenolate affects the fundamental properties of a cluster. 相似文献