Approach to Fully Substituted Cyclic Nitrones from N‐Hydroxylactam Derivatives: Development and Application to the Total Synthesis of Cylindricine C

An approach to cyclic nitrones from N‐hydroxylactam derivatives is documented. The nucleophilic addition of an organolithium reagent to an N‐OSEM [SEM=2‐(trimethylsilyl)ethoxymethyl] lactam forms a five‐membered chelated intermediate, which undergoes both elimination and deprotection to give a fully substituted nitrone in a one‐pot process. When combined with the N‐oxidation of easily available chiral lactams, this method becomes especially useful for the quick synthesis of chiral nitrones in enantio‐pure form, enabling the concise total synthesis of cylindricine C.     

Coupled-Mode Analysis of an NRD-Guide Coupler Based on Singular Perturbation Technique

A coupled-mode formulation for an NRD-guide coupler is presented using the singular perturbation technique. The first-order and second-order perturbations are taken into account in the analysis and the coupled-mode equations based on the eigenmodes of each waveguide in isolation are derived. The propagation constants obtained by these equations are compared with those by the exact theory, conventional coupled-mode theory, and improved coupled-mode theory. The numerical results of present formulation are in good agreement with the exact theory and superior to those of the other formulations.     

Stereoselective synthesis of the beta-anomer of 4'-thionucleosides based on electrophilic glycosidation to 4-thiofuranoid glycals

Three types of 4-thiofuranoid glycal with different 3,5-O-silyl protecting groups were prepared and their electrophilic glycosidation was investigated. The 3,5-bis-O-(tert-butyldimethylsilyl)-4-thiofuranoid glycal (5) was obtained through mesylation of 2-deoxy-4-thio-D-erythro-pentofuranose (4) and subsequent base-promoted elimination, while thermal elimination of sulfoxide derivatives was suitable for the preparation of 3,5-O-(tetraisopropyldisiloxane-1,3-diyl) (9) and 3,5-O-(di-tert-butylsilylene) (11) 4-thioglycals. The glycosidation reactions of these 4-thioglycals were carried out, in the presence of either PhSeCl or NIS, by using silylated derivatives of uracil, thymine, cytosine, and N(6)-benzoyladenine. Among the three 4-thioglycals, 11 was found to be an excellent glycosyl donor, forming the desired beta-anomer exclusively irrespective of the nucleobase employed.     

Refined NMR analysis of the phase structure of solution-crystallized linear polyethylene

Nuclear magnetic resonance (NMR) spectroscopy reveals that solution-grown polyethylene samples have a unique phase structure independent of molecular weight. The lamellar crystallites are composed of about 85% crystalline material with the noncrystalline overlayer as large as 15%. The molecular motion in the overlayer is comparatively hindered and the liquid-like component, which is generally recognized in melt-grown crystals, cannot be produced appreciably, even at 60°C. Such hindered molecular mobility can be understood in terms of a rather restricted conformation of the molecular chains in the noncrystalline overlayer, arising from the special mode of crystallization from dilute solution.     

Anisotropic optical spectra of PrBa2Cu4O8: possible Tomonaga-Luttinger liquid response of the quasi-one-dimensional metallic CuO double chains

The optical spectra of PrBa2Cu4O8 show large in-plane anisotropy. For the a polarization (E perpendicular chain), the spectrum is characterized by a gap of 1.4 eV, indicating the charge-transfer insulating nature of the CuO2 planes. For the metallic chain direction (E // b), the spectrum deviates from a simple Drude response; reflectivity R(b)(omega) shows a sharp edge at approximately 1 eV but it also shows a dip at approximately 15 meV, which splits the conductivity spectrum into two parts--a zero-energy mode with small weight and a pronounced 40 meV mode. These features are discussed in terms of a Tomonaga-Luttinger liquid in a doped 1D Mott insulator and compared with 1D Bechgaard salts.     

Dramatic effects of excess oxygen on physical properties and crystal structure of La0.95Sr0.05MnOy single crystal

We have examined the effects of excess oxygen on the magnetization, electrical transport properties and crystal structure of La_0.95Sr_0.05MnO_y. An antiferromagnetic insulator phase confirmed in the as-grown crystal at low temperatures changed to a ferromagnetic insulator phase after the introduction of excess oxygen. The ferromagnetic transition temperature, T_C, systematically increased with increasing oxygen content, y, due to an increase in the mean valence of manganese. However, the T_C of crystals with excess oxygen was lower than that of the La_1−xSr_xMnO_3.00 having identical manganese valence. This is considered to be a result of the competition among the mean valence of manganese, the concentration of cation vacancies, and the mean ionic radius of cations at the A-site.     

Formal synthesis of (±) —quebrachamine through regio- and stereoselective hydrocyanation of arylallene

This article describes the formal synthesis of quebrachamine based on regio- and stereoselective hydrocyanation of 1,3-disubstituted allenes. Allenyl CC double bonds are effectively discriminated through Ni-catalyzed hydrocyanation and a CN group is utilized as a synthon of piperidine ring. Several steps from HCN adduct afforded known intermediates to quebrachamine.