New odorless method for the Corey-Kim and Swern oxidations utilizing dodecyl methyl sulfide (Dod-S-Me)

Development of the odorless dodecyl methyl sulfide (Dod-S-Me, 1) as an alternative for dimethyl sulfide (DMS) and new odorless methods for the Corey-Kim and Swern oxidations are described. These reactions have been developed with a view toward green chemistry, utilizing Dod-S-Me (1) and common solvents instead of dichloromethane.     

General and practical catalytic enantioselective Strecker reaction of ketoimines: significant improvement through catalyst tuning by protic additives

Significant improvement in enantioselectivity and catalyst activity was achieved for the catalytic enantioselective Strecker reaction. Using a catalyst (1-2.5 mol %) prepared from Gd(OⁱPr)₃ and d-glucose derived ligand 1, and in the presence of 2,6-dimethylphenol as an additive, high enantioselectivity was obtained from a wide range of ketoimines, including heteroaromatic and cyclic ketoimines. The new method was applied to an efficient catalytic asymmetric synthesis of sorbinil, a therapeutic agent for diabetic complications.     

Synthesis and oxidation of bis(triphenylgermyl)zinc

Bis(triphenylgermyl)zinc (Ph₃Ge)₂Zn (1), prepared by the reaction of diethylzinc (Et₂Zn) with two molar amounts of triphenylgermane (Ph₃GeH), was easily reacted by a small amount of oxygen to give tetrameric oxide (Ph₃GeZnO)₄ (2). Four zinc and four oxygen atoms in 2 are arranged such that a cube is formed as determined by X-ray diffraction analysis. Further oxidation of 2 led to the formation of digermoxane, (Ph₃Ge)₂O as a final product.     

Determination of chemical form of antimony in contaminated soil around a smelter using X-ray absorption fine structure.

Only limited information is available about the behavior of antimony (Sb) in contaminated soils. However, understanding the behavior of Sb in contaminated soils is important, because the toxicity or solubility of this element depends on its chemical state. In this study, we investigated the levels of Sb and the chemical forms of Sb in the soil around a smelter using X-ray absorption fine structure (XAFS) spectra. The highest Sb concentration in the contaminated soil was 2900 mg/kg dry soil. According to Sb-K edge X-ray absorption near edge (XANE) spectra, the Sb in the soil was in the form of Sb(V) compounds. The similarity of extended XAFS (EXAFS) spectra suggests that Sb speciation was independent of the sampling site, which indicates that Sb or Sb2O3 emitted from the smelter was converted into Sb(V) compounds in the soil.     

Simultaneous accumulation of both skeletal and appendage-based diversities on tandem Ugi/Diels-Alder products

Diversity-oriented organic synthesis (DOS) is a key concept for construction of skeletally diverse small molecule libraries to discover drug-like small molecules. Here, we describe a DOS class to transform a complex 7-oxanorbornene skeleton, which is readily accessible by a tandem Ugi/Diels-Alder reaction, into two heterotricycle skeletons selectively by using tandem ROM/CM/RCM reaction. In the present study, the mode of cyclization is pre-encoded by building blocks used in the complexity-generating tandem Ugi/Diels-Alder reaction. Since variable alkenes can be used in the CM reaction, our approach can be extended to construct both skeleton- and appendage-diverse small molecule libraries.     

Objective measurement of minimal erythema and melanogenic doses using natural and solar-simulated light

Very little information exists on the amount of natural and artificial UV light required to cause sunburn and tanning in individuals with very pale skin who are at the greatest risk of developing skin cancer. We have investigated minimal erythema dose (MED) and minimal melanogenic dose (MMD) in a group of 31 volunteers with Fitzpatrick skin types I and II using an Oriel 1000 W xenon arc solar simulator and natural sunlight in Sydney, Australia. We measured the erythemal and melanogenic responses using conventional visual scoring, a chromameter and an erythema meter. We found that the average MED measured visually using the artificial UV source was 68.7 +/- 3.3 mJ/cm2 (3.4 +/- 0.2 standard erythema doses [SED]), which was significantly different from the MED of sunlight, which was 93.6 +/- 5.6 mJ/cm2 (P < 0.001) (11.7 +/- 0.7 SED). We also found significant correlations between the solar-simulated MED values, the melanin index (erythema meter) and the L* function (chromameter). The average MMD (obtained in 16 volunteers only) using solar-simulated light was 85.6 +/- 4.9 mJ/cm2, which was significantly less than that measured with natural sunlight (118.3 +/- 8.6 mJ/cm2; P < 0.05). We mathematically modeled the data for both the chromameter and the erythema meter to see if we were able to obtain a more objective measure of MED and differentiation between skin types. Using this model, we were able to detect erythemal responses using the erythema index function of the erythema meter and the a* function of the chromameter at lower UV doses than either the standard visual or COLIPA methods.     

Skeletal diversity by allylation/RCM on Ugi four-component coupling reaction products

Here, we report a diversity-oriented synthetic approach toward skeletally diverse, cyclized peptidomimetics with diverse appendages. Starting from α-(N-acylamino)amides with various appendages, 12 to 16-membered lactams with defined olefin geometry were synthesized by a common synthetic sequence. We also synthesized the macrocycle in a liquid phase directed toward a construction of the peptidomimetics library.     

Motor protein nano-biomachine powered by self-supplying ATP

A new nano-biomachine has been created from microtubules (MTs) and hetero-bifunctional polymer particles bearing pyruvate kinase, which is propelled on glass surfaces coated with kinesin by use of self-supplying ATP.     

NOx-Sorbing Metal Oxides, MnOx–CeO2. Oxidative NO Adsorption and NOx–H2 Reaction

(n)MnO_x–(1?n)CeO₂ binary oxides have been studied for the sorptive NO removal and subsequent reduction of NO_x sorbed to N₂ at low temperatures (≤150 °C). The solid solution with a fluorite-type structure was found to be effective for oxidative NO adsorption, which yielded nitrate (NO^? ₃) and/or nitrite (NO^? ₂) species on the surface depending on temperature, O₂ concentration in the gas feed, and composition of the binary oxide (n). A surface reaction model was derived on the basis of XPS, TPD, and DRIFTS analyses. Redox of Mn accompanied by simultaneous oxygen equilibration between the surface and the gas phase promoted the oxidative NO adsorption. The reactivity of the adsorbed NO_x toward H₂ was examined for MnO_x–CeO₂ impregnated with Pd, which is known as a nonselective catalyst toward NO–H₂ reaction in the presence of excess oxygen. The Pd/MnO_x–CeO₂ catalyst after saturated by the NO uptake could be regenerated by micropulse injections of H₂ at 150 °C. Evidence was presented to show that the role of Pd is to generate reactive hydrogen atoms, which spillover onto the MnO_x–CeO₂ surface and reduce nitrite/nitrate adsorbing thereon. Because of the lower reducibility of nitrate and the competitive H₂–O₂ combustion, H₂–NO reaction was suppressed to a certain extent in the presence of O₂. Nevertheless, Pd/MnO_x–CeO₂ attained 65% NO-conversion in a steady stream of 0.08% NO, 2% H₂, and 6% O₂ in He at as low as 150 °C, compared to ca. 30% conversion for Pd/γ–Al₂O₃ at the same temperature. The combination of NO_x-sorbing materials and H₂-activation catalysts is expected to pave the way to development of novel NO_x-sorbing catalysts for selective deNO_x at very low temperatures.     

1,2,4-Triazines, 9. The synthesis of novel 4-amino-1,6-dihydro-1,2,4-triazinones

3-Alkylthio-4-amino-1,6-dihydro-1,2,4-triazin-5(4H)-ones were synthesized by the reduction of 3-thio-4-amino-1,2,4-triazine-3,5(2.H,4H)-diones and successive S-alkylation. The regiospecific alkylation on the N-1 position or the exo amino group leads to a variety of 1,6-dihydro-1,2,4-triazin-5(4H)-one derivatives. An alternative synthesis of 3-thio-4-amino-1,6-dihydro-1,2,4-triazine-3,5(2H,4H)-diones was accomplished through the cyclization of 1-thiocarbohydrazidoacetamide derivatives.