Highly Chemoselective Aerobic Oxidation of Amino Alcohols into Amino Carbonyl Compounds

The direct oxidation of unprotected amino alcohols to their corresponding amino carbonyl compounds has often posed serious challenges in organic synthesis and has constrained chemists to adopting an indirect route, such as a protection/deprotection strategy, to attain their goal. Described herein is a highly chemoselective aerobic oxidation of unprotected amino alcohols to their amino carbonyl compounds in which 2‐azaadamantane N‐oxyl (AZADO)/copper catalysis is used. The catalytic system developed leads to the alcohol‐selective oxidation of various unprotected amino alcohols, carrying a primary, secondary, or tertiary amino group, in good to high yield at ambient temperature with exposure to air, thus offering flexibility in the synthesis of nitrogen‐containing compounds.     

First total synthesis of artepillin C established by o,o'-diprenylation of p-halophenols in water

We have demonstrated that prenylation of p-halophenols was dependent on the solvent effect and succeeded in o,o'-diprenylation of p-halophenols in water. Following the Mizoroki-Heck coupling of the diprenyl-p-iodophenol 3c with methyl acrylate and then hydrolysis, we first synthesized artepillin C [3-(4-hydroxy-3,5-di(3-methyl-2-butenyl)phenyl)-2(E)-propenoic acid] (1), which is a biologically active constituent of propolis. These reactions may be applicable to the synthesis of various useful natural products such as 2,4,6-trisubstituted phenol derivatives.     

Normal stress and shear stress in a viscoelastic liquid under steady shear flow: Effect of molecular weight heterogeneity

Under steady shear flow, the normal stress and the shear stress in both dilute and concentrated solutions of monodisperse poly-α-methylstyrenes and their blends were measured. It was confirmed that the molecular theories of Rouse and Zimm extended to concentrated solutions can explain the relation between the zero-shear normal stress coefficient and the zero-shear steady-flow viscosity for both monodisperse and polydisperse systems. Shear-rate dependence of steady-flow viscosity can be understood fairly well by the molecular entanglement concept proposed by Graessley so long as the polymer is monodisperse or the amount of the higher molecular weight component is high. However, zero-shear viscosity of blended systems cannot be explained quantitatively by the theory of Graessley. The shear-rate dependence of steady-state compliance of blended systems was also observed, and it can well be explained by the theory of Tanaka, Yamamoto, and Takano which interpreted the shear rate-dependent steady-state compliance in terms of the relaxation time spectrum and its variation with shear rate.     

Metal-insulator transition investigation in V2O3 by nuclear magnetic resonance and relaxation

The high temperature metal-insulator transition in pure V₂O₃ has been investigated by nuclear magnetic resonance and relaxation. The relaxation rate in the range 160–320K was found to satisfy the Korringa relaxation and at temperature above 550K to be constant as expected for a paramagnetic insulator. In the intermediate temperature range the high field resonance line shape showed broadening which we interpret as due to the coexistence of a metallic and an insulating phase.     

Palladium-indium iodide-mediated allylation and propargylation of glyoxylic oxime ether and hydrazone: the role of water in directing the diastereoselective allylation

Allylation and propargylation of glyoxylic oxime ether in the presence of a catalytic amount of palladium(0) complex and indium(I) iodide were studied. Excellent diastereoselectivities in allylation were achieved in the presence of water, although low diastereoselectivities were observed in the absence of water. Propargylation of glyoxylic oxime ether proceeded with good diastereoselectivities in the presence of LiBr or LiCl.     

An HPLC assay of hydroxyl radicals by the hydroxylation reaction of terephthalic acid

An HPLC assay for hydroxyl radicals is described. The hydroxyl radical was trapped by terephthalic acid (non-fluorescent), and 2-hydroxyl terephthalic acid (fluorescent) was quantitated by HPLC-fluorescence detection. At a terephthalic acid concentration of 4.25 mmol/L, the hydroxyl radical formed in the Fenton reaction was successfully assayed in the concentration range of hydrogen peroxide of 2.5-50 micro mol/L, where the concentration of Fe(II) was 50 micro mol/L. The fluorescence of 2-hydroxy terephthalate was stable at 24 h, and its detection limit by this method was 5 nmol/L (100 fmol).