Determination of the absolute structure of (+)-akaterpin

We describe the total synthesis and structural determination of (+)-akaterpin (1), an inhibitor of phosphatidylinositol-specific phospholipase C (PI-PLC). The key features of the synthetic strategy include the resolution of β,γ-unsaturated ketone (±)-2a with chiral sulfoximine 6. The absolute stereochemistry was determined by comparison of the specific optical rotation data of (+)-1 and (-)-1 with that of natural akaterpin.     

Practical access to the polymer incarcerated platinum (PI Pt) catalyst and its application to hydrogenation

Polymer incarcerated platinum catalysts (PI Pt) were conveniently prepared from PtCl(2)(COD) or H(2)PtCl(6).6H(2)O and styrene copolymers via reduction of the Pt sources with triethylamine, coacervation, and cross-linking. The Pt catalysts have been successfully applied to catalytic hydrogenation including saturation of heterocyclic compounds.     

Practical preparation method of polymer-incarcerated (PI) palladium catalysts using Pd(II) salts

[reaction: see text]. Polymer-incarcerated (PI) palladium catalyst was practically prepared from inexpensive Pd(II) salts and a polystyrene-based copolymer under reducing conditions. Remarkable effects of alkali metal salts on the palladium loading were observed. PI Pd thus prepared showed high catalytic activity in Mizoroki-Heck reactions and Suzuki-Miyaura couplings with a range of substrates including an aryl chloride. In all cases, the Pd catalyst was recovered quantitatively without leaching, and reused several times without significant loss of activity.     

Electrochemical reduction of nitrate using various anodes and a Cu/Zn cathode

Electrochemical reduction of nitrate was studied using a Cu/Zn cathode and Ti/Pt, Ti/IrO₂–Pt and Ti/RuO₂–Pt anodes in an undivided and unbuffered cell. A novel condition for performing both cathodic reduction of nitrate and anodic oxidation of the ammonia and nitrite by-products was achieved using Ti/Pt and Ti/IrO₂–Pt anodes in the presence of NaCl, especially with Ti/IrO₂–Pt anode. Nitrate could be completely removed using the Ti/IrO₂–Pt and Ti/Pt anode, with neither ammonia nor nitrite detected in the treated solution. A low nitrate reduction rate was observed when using a Ti/RuO₂–Pt anode in the presence of NaCl. However, in the absence of NaCl, all anodes showed good performance for nitrate reduction, with the Ti/Pt anode having the highest selectivity for reducing nitrate to nitrogen.     

Dual of two dimensional Lorentz sequence spaces

In [M. Kato and L. Maligranda, On James and Jordan–von Neumann constants of Lorentz sequence spaces, J. Math. Anal. Appl. 258 (2001) 457–465], it is an open problem to compute the James constant of the dual space of two dimensional Lorentz sequence space d⁽²⁾(w,q). In this paper, we shall determine the dual norm of d⁽²⁾(w,q) and completely compute the James constant of d⁽²⁾(w,q).     

Inverted meso-aryl porphyrins with heteroatoms; characterization of thia, selena, and oxa N-confused porphyrins.

Synthesis and characterization of inverted porphyrins containing S, Se, and O are reported. A simple 3 + 1 MacDonald-type condensation using modified tripyrrane containing the N-confused ring and diols afforded various N-confused porphyrins 6a-f in 19-30% yield. The single-crystal X-ray structure of 6b shows a ruffled conformation with tilt angles of 21.11 degrees and 31.23 degrees for the N-confused ring and the adjacent pyrrole ring III, respectively, revealing its severe nonplanarity. Significant changes in C alpha-C beta, C beta-C beta, and C alpha-X bond lengths are observed in 6b relative to free thiophene and pyrrole, suggesting the altered delocalization pathway in the modified N-confused porphyrins. The two molecules in the unit cell show a cyclophane-type noncovalent dimer with a face to face orientation of two N-confused pyrrole rings as a result of the presence of weak N-H...N and C-H...N intermolecular hydrogen bonds involving pyrrole-NH, the N atom of the N-confused ring, and the C atom of the pyrrole ring. A detailed 1H and 13C NMR study by 1D and 2D methods allowed assignments of all the peaks in the free base and protonated forms. NMR studies reveal the presence of three different tautomeric forms in solution for 6c in CDCl3 at low temperature. UV-visible studies reveal absorption band shifts upon heteroatom substitution, and the magnitudes of these shifts are dependent on the nature of the heteroatom. In all cases both monoprotonated and diprotonated species have been identified, and on addition of acid, the first proton goes to the outer N2 atom of the N-confused ring.     

Molecular Structure and Mutual Recognition Between Host and Guest Molecules Found in the Crystal Structures of Oxacalix[4]arenes Complexed with Xylene Isomers

The crystal structures of two complexes of oxacalix[4]arene derivatives {p-isopropyl-dihomooxacalix[4]arene (IOC-4)and p-tert-butyldihomooxacalix[4]arene(BOC-4)} with xylene isomers have been determined byX-ray diffraction method. Furthermore, in order toestimate the strength of the mutual interactionsbetween host (IOC-4 and BOC-4) and guest (o-, m-and p-xylene), the heat of complex formation forthe IOC-4 : xylene complexes was calculated using a molecularorbital method, and a differential scanningcalorimetric investigation was performed forthe BOC-4 : xylene complexes.     

Lewis Acid Catalyzed Ring‐Opening Reactions of Sugar‐Derived Semicyclic N,O‐Acetals

N‐(Alkoxycarbonyl)‐N‐glycosides (polyoxygenated semicyclic N,O‐acetals) were efficiently synthesized from regular acetyl or methyl glycosides (glucopyranoside, ribofuranoside, arabinofuranoside, and 2‐deoxyribofuranoside) and a carbamate by treatment of trimethylsilyl trifluoromethanesulfonate and 4 Å molecular sieves. It was found that these N‐glycosides underwent Lewis acid catalyzed ring‐opening reactions with silylated nucleophiles to give ring‐opened amino alcohols with good‐to‐high diastereoselectivity. The reactivity order, 2‐deoxyribofuranoside > arabinofuranoside > ribofuranoside > glucopyranoside, was revealed. Ring‐opening reductions were also investigated with silanes or diisobutylaluminium hydride. An appropriate reducing agent was found to be dependent on the N‐glycosides used. A glycosidase inhibitor, (2S,3R,4R)‐2‐hydroxymethylpyrrolidine‐3,4‐diol ( 7 ) was synthesized by means of the reactions.     

Simulation on double-ring-resonator-type device considering gain for heat-assisted magnetic recording

Optical Review - Heat-assisted magnetic recording (HAMR) is a promising technology for improving the recording density of hard disk drives. A near-field transducer (NFT), which forms a small light...