New efficient organic activators for highly enantioselective reduction of aromatic ketones by trichlorosilane

[reaction: see text] Aryl ketones were reduced to the corresponding alcohols with excellent enantioselectivity (up to 99.7% ee) by Cl3SiH in the presence of a catalytic amount of N-formyl-alpha'-(2,4,6-triethylphenyl)-L-proline as an activator. Both carboxyl group at the alpha-position of the activator and 2,4,6-triethylphenyl group at the alpha'-position were critical for the high enantioselectivity.     

High static pressure alters spin trapping rates in solution. Dependence on the structure of nitrone spin traps

Using a competitive spin trapping method, relative spin trapping rates were quantified for various short-lived radicals (methyl, ethyl, and phenyl radicals). High static pressure was applied to the competitive spin-trapping system by employing high-pressure electron spin resonance (ESR) equipment. Under high pressure (490 bar), spin trapping rate constants for alkyl and phenyl radicals increased by 10 to 40%, and the increase was dependent on the structure of nitrone spin traps. A maximum increase was obtained when tert-butyl(4-pyridinylmethylene)amine N-oxide (4-POBN) was used as a spin trap. Activation volumes (DeltaDeltaV(double dagger)) for the two spin trapping reactions were calculated to be -17-(-9) cm(3) mol(-1) for the 4-POBN system.     

Medicinal Flowers. Part 29. Acylated Oleanane‐Type Triterpene Bisdesmosides: Perennisaponins G,H, I,J, K,L, and M with Pancreatic Lipase Inhibitory Activity from the Flowers of Bellis perennis

The MeOH extract from the flowers of Bellis perennis was found to show pancreatic‐lipase inhibitory activity (IC₅₀ 455 μg/ml). From the extract, seven new triterpene saponins named perennisaponins G ( 1 ; IC₅₀ 163 μM ), H ( 2 ; 137 μM ), I ( 3 ; 147 μM ), J ( 4 ; 148 μM ), K ( 5 ; 223 μM ), L ( 6 ; 81.4 μM ), and M ( 7 ; 195 μM ) were isolated as pancreatic lipase inhibitors. The stereostructures of 1 – 7 were elucidated on the basis of chemical and spectroscopic evidence.     

Competitive Trapping of Nitric Oxide (NO) Between Fe(III)-dithiocarbamate Complex and Liposome-encapsulated Trimethylammonio-PTIO: Effects of Ligand Structure, Charge on Liposome Surface, and External Pressure on NO-trapping Rates

Using a competitive nitric oxide (NO)-trapping method between Fe–dithiocarbamate (DTC) complexes and liposome-encapsulated 2-[4-trimethylammonio]-4,4,5,5-tetramethyl-imidazoline-1-oxyl 3-oxide (TMAPTIO), NO-trapping rates of Fe–DTC complexes in the presence of phosphatidylcholine liposomes were quantified for five kinds of Fe–DTC complexes. We investigated how the DTC ligand structure influences the NO-trapping rates of Fe–DTC complexes. The negatively charged liposomes give a higher NO-trapping rate of Fe–DTC complexes than do the positively charged ones, suggesting that the presence of a charge on the liposome surface affects the NO-trapping rate processes of Fe–DTC complexes. In addition, on the basis of the pressure dependence experiments for the competitive reaction, we evaluated the difference in activation volumes between the NO-trapping reactions by Fe–DTC complexes and TMA-PTIO, which allowed us to consider possible reaction mechanisms for the NO-trapping processes.     

Two‐factors each component of which contains a specified vertex

It is shown that if G is a graph of order n with minimum degree δ(G), then for any set of k specified vertices {v₁,v₂,…,v_k} ? V(G), there is a 2‐factor of G with precisely k cycles {C₁,C₂,…,C_k} such that v_i ∈ V(C_i) for (1 ≤ i ≤ k) if or 3k + 1 ≤ n ≤ 4k, or 4k ≤ n ≤ 6k ? 3,δ(G) ≥ 3k ? 1 or n ≥ 6k ? 3, . Examples are described that indicate this result is sharp. © 2003 Wiley Periodicals, Inc. J Graph Theory 43: 188–198, 2003     

Synthesis of 2,4-disubstituted thiazoles from (Z)-(2-acetoxyvinyl)phenyl-lambda3-iodanes: nucleophilic substitution of alpha-lambda3-iodanyl ketones with thioureas and thioamides

In the presence of triethylamine, (Z)-(2-acetoxy-1-alkenyl)phenyl-lambda(3)-iodanes react with thioureas or thioamides in MeOH to give 2,4-disubstituted thiazoles directly in good yields. The reaction probably involves generation of highly reactive alpha-lambda(3)-iodanyl ketones through ester exchange of the beta-acetoxy group with liberation of methyl acetate, followed by nucleophilic substitutions with thioureas or thioamides.     

Photoinduced methanol formation from methane and no at 275 k on highly dispersed vanadium oxide supported on vycor glass and its reaction intermediate species

UV irradiation at 275 K of the highly dispersed V/Vycor oxide catalyst in the presence of NO leads to the formation of N₂ and O₂. The decomposition reaction of NO proceeds photocatafytically. In the presence of CH₄, UV-irradiation of the catalyst at 275 K leads to the formation of C₂H₆ and C₂H₄, but this reaction is found to accompany the reduction of the catalyst as well as the formation of CH₃ radicals. A dynamic photoluminescence study of the catalyst in the absence and presence of the reactants indicates that the charge transfer excited triplet state of the surface vanadyl-species (V=O) plays a significant role in these photoinduced reactions of NO and CH₄. On the other hand, UV-irradiation of the catalyst at 275 K in the presence of a mixture of NO and CH₄ leads to the formation of CH₃OH in addition to the above products. The higher the ratio of NO/CH₄ in the mixture is, the larger the yield of CH₃OH becomes and the smaller the yields of C₂H₆ and C₂H₄ become, the reaction proceeding catalytically. Thus, the present results not only imply that the highly dispersed supported vanadium oxide catalysts can be utilized as a potential photocatalyst for de-NOx-ing and/or methane activation at normal temperature but also suggest that the photo-formed oxygen species from NO molecules plays a significant role in the photoinduced CH₃OH formation from CH₄ and NO on V/Vycor oxide catalysts at 275 K.     

Synthesis and properties of highly fluorescent indolizino[3,4,5-ab]isoindoles

We report here the synthesis, X-ray structures, optical and electrochemical properties, fabrication of light-emitting devices, and density functional calculations for indolizino[3,4,5-ab]isoindole (INI) derivatives. Strongly luminescent heterocycles based on the INI unit were synthesized by 1,3-dipolar cycloaddition reactions between pyrido[2,1-a]isoindole (PIS) and acetylene or ethylene derivatives. They are indolizino[3,4,5-ab]isoindoles 2-9 and 14-15, benzo[1',2'-1,2]indolizino[3,4,5-ab]isoindoles 10, pyridazino[4',5':1,2]indolizino[3,4,5-ab]isoindoles 12-13, and 2,3-hydropyridazino[4',5':1,2]indolizino[3,4,5-ab]isoindole-1,4-dione 11. The relative luminescence quantum yield can be as high as 90%. Their reduction and oxidation potentials and high luminescence can make these heterocycles possible alternatives to tris(8-hydroxyquinolinato)aluminum (Alq(3)). The brightness of the light-emitting device reached as high as 10(4) cd/m(2) and indolizino[3,4,5-ab]isoindole 3 emits beautifully blue light. The X-ray crystal structures of INI derivatives were obtained for the first time. The geometries obtained from X-ray data and density functional theory calculations shed more light on an interesting formally antiaromatic 16pi system, which is divided into 10pi and 6pi aromatic systems. We also report a relatively easy protonation of INI, which occurs at a carbon, rather than nitrogen atom.     

Vertex-Disjoint Cycles Containing Specified Edges

Dirac and Ore-type degree conditions are given for a graph to contain vertex disjoint cycles each of which contains a previously specified edge. One set of conditions is given that imply vertex disjoint cycles of length at most 4, and another set of conditions are given that imply the existence of cycles that span all of the vertices of the graph (i.e. a 2-factor). The conditions are shown to be sharp and give positive answers to conjectures of Enomoto in [3] and Wang in [5]. Revised: July 28, 1999     

Thin-film poly-Si solar cells on glass substrate fabricated at low temperature

The performances of thin-film poly-Si solar cells with a thickness of less than 5 μm on a glass substrate have been investigated. The cell of glass/back reflector/n-i-p type Si/ITO is well characterized by the structure of naturally surface texture and enhanced absorption with a back reflector (STAR), where the active i-type poly-Si layer was fabricated by plasma chemical vapor deposition (CVD) at low temperature. The cell with a thickness of 2.0 μm demonstrated an intrinsic efficiency of 10.7% (aperture 10.1%), an open-circuit voltage of 0.539 V and a short-current density of 25.8 mA/cm² as independently confirmed by Japan Quality Assurance. No light-induced degradation is observed. The optical and transport properties of poly-Si cells are summarized. Received: 1 March 1999 / Accepted: 28 March 1999 / Published online: 7 July 1999