Direct Addition of Amides to Glycals Enabled by Solvation‐Insusceptible 2‐Haloazolium Salt Catalysis

The direct 2‐deoxyglycosylation of nucleophiles with glycals leads to biologically and pharmacologically important 2‐deoxysugar compounds. Although the direct addition of hydroxyl and sulfonamide groups have been well developed, the direct 2‐deoxyglycosylation of amide groups has not been reported to date. Herein, we show the first direct 2‐deoxyglycosylation of amide groups using a newly designed Brønsted acid catalyst under mild conditions. Through mechanistic investigations, we discovered that the amide group can inhibit acid catalysts, and the inhibition has made the 2‐deoxyglycosylation reaction difficult. Diffusion‐ordered two‐dimensional NMR spectroscopy analysis implied that the 2‐chloroazolium salt catalyst was less likely to form aggregates with amides in comparison to other acid catalysts. The chlorine atom and the extended π‐scaffold of the catalyst played a crucial role for this phenomenon. This relative insusceptibility to inhibition by amides is more responsible for the catalytic activity than the strength of the acidity.     

A Hydroperoxide-Mediated Decarboxylation of α-Ketoacids Enables the Chemoselective Acylation of Amines

Strategies for the formation of amide bonds, that is, one of the most basic and important transformations in organic synthesis, have so far focused predominantly on dehydration reactions. Herein, we report and demonstrate the practical utility of a novel decarboxylative amidation of α-ketoacids by using inexpensive tert-butyl hydroperoxide (TBHP), which is characterized by high yields, a broad substrate scope, mild reaction conditions, and a unique chemoselectivity. These features enable the synthesis of peptides from amino acid derived α-ketoacids under preservation of the stereochemical information.     

When does the subadditivity theorem for multiplier ideals hold?

Demailly, Ein and Lazarsfeld proved the subadditivity theorem for multiplier ideals on nonsingular varieties, which states the multiplier ideal of the product of ideals is contained in the product of the individual multiplier ideals. We prove that, in the two-dimensional case, the subadditivity theorem holds on log terminal singularities. However, in the higher dimensional case, we have several counterexamples. We consider the subadditivity theorem for monomial ideals on toric rings and construct a counterexample on a three-dimensional toric ring.

     

Anomalies of ultrasonic velocity in high-Tc ceramics YBa2Cu3Oy and BiSrCaCu2Oy

Ultrasonic longitudinal velocity and adsorption have been measured in ceramic superconductors YBa₂Cu₃O_y with various porosity and also in BiSrCaCu₂O_y. A velocity drop of about 400 ppm was found at T_c only in the measurements on cooling. The magnitude of the velocity drop is anomalously large compared with the value expected from the thermodynamics. A hysteresis of velocity with respect to temperature was observed in all the samples studied. It is suggested that some structural change at pore size level is responsible for this phenomenon.     

Magnetism in electron-doped copper oxides

We report muon spin relaxation/rotation measurements on sintered powder samples of Nd_2−x Ce _x CuO_4−y and a large single crystal of Nd₂CuO_4−y . We find an electronic phase diagram which is quite similar to that of hole-doped superconductors such as La_2−x Sr _x CuO_4−y , although the doping of electrons into the system is less efficient in destroying the static moments on the copper spins. Static magnetic order in Nd₂CuO_4−y appears below about 250 K, and two spin reorientations are seen atT=75 K andT=35 K. Measurements of the magnetic field penetration depth have been unsuccessful due to the rare-earth paramagnetism of these materials.     

Comparative studies of the colony-promoting activity of porcine kidney extract with several interleukins and colony-stimulating factors.

Porcine kidney extracts (PKE) possess colony-promoting activity (CPA) which stimulates primitive hematopoietic cells in the presence of granulocyte/macrophage colony-stimulating factor (GM-CSF), but PKE itself does not stimulate colony formation on murine bone marrow cells. We have compared the CPA of PKE with that of recombinant cytokines or CSFs such as interleukin-1 alpha (IL-1 alpha), IL-3, IL-6, granulocyte colony-stimulating factor (G-CSF), GM-CSF and macrophage colony-stimulating factor (CSF-1). All of these factors were less potent than PKE. Furthermore, the combinations of IL-1 alpha or PKE with G-CSF, GM-CSF, IL-3 or IL-6 were examined in the presence of one of these factors such as CSF. It is found that PKE acts synergistically with G-CSF, GM-CSF, IL-3 and IL-6, showing enhancement ratios of 10, 2.5, 4.2 and 30, respectively. The combination of IL-1 alpha resulted in poor colony formation in contrast with those of PKE, except for CSF-1. These results suggest that the CPA of the factor(s) in PKE differ from the cytokines and CSFs tested in this study, and is significantly affected by various types of CSF.