Asymmetric alkylation of carboxyamides by using trans-2,5-disubstituted pyrrolidines as chiral auxiliaries

trans-2,5-Bis(methoxymethyl)- and trans-2,5-bis(methoxymethoxymethyl)pyrrolidines proved to be excellent chiral auxiliaries for the asymmetric alkylation of the corresponding carboxyamide enolates giving good chemical yield and high stereoselectivity (invariably over 95% de), with remarkable flexibility to substrates and reaction conditions.     

Lewis acid-catalyzed propargylic etherification and sulfanylation from alcohols in MeNO₂-H₂O

Direct scandium- and lanthanum-catalyzed etherifications of propargyl alcohols 1 and 6 in MeNO?-H?O provided propargyl ethers 3, 4 and 7 in high yields. In addition, reactions of 1 and 6 with thiols exclusively yielded the corresponding propargyl sulfides.     

Efficient iron-mediated approach to pyrano[3,2-a]carbazole alkaloids--first total syntheses of O-methylmurrayamine A and 7-methoxymurrayacine, first asymmetric synthesis and assignment of the absolute configuration of (-)-trans-dihydroxygirinimbine

Iron-mediated oxidative cyclisation provides an efficient approach to pyrano[3,2-a]carbazole alkaloids. Thus, improved routes to girinimbine and murrayacine as well as the first total syntheses of O-methylmurrayamine A and 7-methoxymurrayacine are reported. Asymmetric epoxidation of girinimbine led to (-)-trans-dihydroxygirinimbine and the assignment of its absolute configuration.     

Electrochemical detection for dynamic analyses of a redox component in droplets using a local redox cycling-based electrochemical (LRC-EC) chip device

This report describes the electrochemical detection of a redox component in droplets using a local redox cycling-based electrochemical (LRC-EC) chip device consisting of 256 sensors. The time-course analyses showed that the redox compound in the droplet was dynamically changed during droplet evaporation or mass transfer through a water/oil interface.     

Electronic structures of chemisorption systems on Si(111) surface I. Si(111)7 × 7/H,Cl

Electronic structures of chemisorption on Si(111)/H,C1 are investigated by the first principle DV-Xα cluster method. The calculations are carried out for chemisorption on different sites, based on the Si₁₃H₁₅ cluster, and the effect of surface vacancy and buckling on the electronic structure is examined in detail. The present calculation shows that the Si₁₃H₁₅ surface cluster reproduces very well the more sophisticated band calculation for the Si(111) surface. It is concluded that the vacancy model with chemisorbed atoms at appropriate sites is reasonable to interpret the observed UPS of Si(111) 7 × 7/H,C1. The charge transfer between the substrate atom and the adatom depends strongly both on the chemisorption sites and on the electronegativitv difference.     

Formation and lithuim ionic conduction of the antifluorite type solid electrolytes,Li2+x-y-z[(NH)1-x-y-zNxClyHz]

Antifluorite type solid electrolytes, Li_2+x-y-z[(NH)_1-x-y-zN_xCl_yH_z] have been synthesized from Li₃N, LiCl and LiCl·H₂O or $\text{Li}{}_2\text{[(}\text{NH}\text{)}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{N}{}_{\mathrm{<mtext>1</mtext><mtext>4</mtext>}}\text{H}{}_{\mathrm{<mtext>1</mtext><mtext>4</mtext>}}$]. Either of the last two compounds introduces NH^2- ions into the product and is indispensable to form the antifluorite type structure. The lattice parameter decreases with increasing amount of NH^2- ions in the compound, reflecting the difference of anion sizes between Cl^- and NH^2- ions. Activation energies of Li⁺ diffusive motion, derived from both conductivity and NMR measurements, increase with concentration of NH^2- ions, although the values differ by a factor of ≈2 netween the both methods.     

HPLC separation of triacylglycerol positional isomers on a polymeric ODS column

A polymeric ODS column was applied to the resolution of triacylglycerol positional isomers (TAG-PI), i.e. 1,3-dioleoyl-2-palmitoyl-glycerol (OPO) and 1,2-dioleoyl-3-palmitoyl-rac-glycerol (OOP), with a recycle HPLC system. To investigate the ODS column species and the column temperatures for the resolution of a TAG-PI pair, a mixture of OPO and OOP was subjected to an HPLC system equipped with a non-endcapped polymeric, endcapped monomeric, endcapped intermediate, or non-endcapped monomeric ODS column at three different column temperatures (40, 25, or 10 degrees C). Only the non-endcapped polymeric ODS column achieved the separation of OPO and OOP, and the lowest column temperature (10 degrees C) showed the best resolution for them. The other pair of TAG-PI, a mixture of 1,3-dipalmitoyl-2-oleoyl-glycerol (POP) and 1,2-dipalmitoyl-3-oleoyl-rac-glycerol (PPO) was also subjected to the system equipped with a non-endcapped polymeric or monomeric ODS column at five different column temperatures (40, 32, 25, 17, and 10 degrees C). Thus, POP and PPO were also separated on only the non-endcapped polymeric ODS column at 25 degrees C. However, no clear peak appeared at 10 degrees C. These results would indicate that the polymeric ODS stationary phase has an ability to recognize the structural differences between TAG-PI pairs. Also, the column temperature is a very important factor for separating the TAG-PI pair, and the optimal temperature would relate to the solubility of TAG-PI in the mobile phase. Furthermore, the recycle HPLC system provided measurements for the separation and analysis of TAG-PI pairs.