A Hydroperoxide-Mediated Decarboxylation of α-Ketoacids Enables the Chemoselective Acylation of Amines

Strategies for the formation of amide bonds, that is, one of the most basic and important transformations in organic synthesis, have so far focused predominantly on dehydration reactions. Herein, we report and demonstrate the practical utility of a novel decarboxylative amidation of α-ketoacids by using inexpensive tert-butyl hydroperoxide (TBHP), which is characterized by high yields, a broad substrate scope, mild reaction conditions, and a unique chemoselectivity. These features enable the synthesis of peptides from amino acid derived α-ketoacids under preservation of the stereochemical information.     

Optimization of the surface texture for silicon carbide sliding in water

Surface texturing has been recognized as an effective means to improve the tribological performances of sliding surfaces. Usually, generation additional hydrodynamic pressure to increase the load carrying capacity is regarded as the most significant effect of surface texture. In the case of silicon carbide sliding against identical material in water, the experimental results indicate that surface texture is also helpful to improve the running-in progress to smooth the contact surfaces, showing another reason to result in low friction. Based on the consideration of enhancing the generation of hydrodynamic pressure and improving running-in progress, a surface texture pattern, which was combined with large (circle, 350 μm in diameter) and small (rectangular, 40 μm in length) dimples, was designed to maximize the texture effect on the load carrying capacity of SiC surfaces sliding in water. The friction coefficient of such textured surface was evaluated and compared with that of untextured and those only with large or small dimples only. The friction reduction mechanisms of the patterns with different dimples in size are discussed.     

Stereological simulations of asymmetric polymerization in channels of bile acid inclusion compounds: A detailed analysis of the monomer arrangements in the channels

We studied simulations by computer graphics to estimate the steric mechanism of the asymmetric polymerization of prochiral diene monomers in channels of inclusion compounds of steroidal bile acids, such as deoxycholic acid (DCA) and cholic acid. We applied a hierarchization method to interpret the crystal structures of bile acids, clarifying that the chiral host molecules associated to form characteristic 2₁-helical assemblies with uneven surfaces. A detailed analysis of the uneven channels in a close-packing state indicated that there were many possible arrangements of the monomers in the channels. The plausible arrangements in the channel could explain a previous study, which showed that the polymerization in the DCA channel yielded chiral polymers with a predominant configuration from prochiral diene monomers, such as 2-methyl-trans-1,3-pentadiene. On the basis of such simulation studies of the arrangements of guest monomers in the channel, we examined a plausible steric mechanism for asymmetric inclusion polymerization. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4648–4655, 2004     

Facilitated sulfate transfer across the nitrobenzene-water interface as mediated by hydrogen-bonding ionophores.

Facilitated SO4(2-) transfers by hydrogen bond-forming ionophores are investigated across the nitrobenzene (NB)-water interface by using polarography with a dropping electrolyte electrode. Bis-thiourea 1, alpha,alpha'-bis(N'-p-nitrophenylthioureylene)-m-xylene, is found to significantly facilitate the transfer of the highly hydrophilic SO4(2-) whereas its counterpart, N-(p-nitrophenyl)-N'-propylthiourea (ionophore 2), cannot. In contrast to the predominant formation of a 1:1 complex with SO4(2-) in the bulk NB phase, the SO4(2-) transfer assisted by 1 is indeed based on the formation of a 1:2 complex between SO4(2-) and ionophore, even under the condition of [SO4(2-)]aq > [1]org. Such an exclusive formation of the 1:2 (SO4(2-) to ionophore) complex at the NB-water interface is not observed with structurally similar bis-thiourea 3, alpha,alpha'-bis(N'-phenylthioureylene)-m-xylene, where p-nitrophenyl moietes of bis-thiourea 1 are simply replaced by phenyl groups. The facilitated transfer of SO4(2-) with bis-thiourea 1 is further compared to that of HPO4(2-) and H2PO4- across the NB-water interface, which was previously shown to be assisted by 1 through the formation of the 1:1 and 2:1 (anion to ionophore) complexes, respectively. On the basis of these examinations, unique binding behaviors of hydrogen bond-forming ionophores at the NB-water interface are discussed, with a view towards development of ionophore-based anion-selective chemical sensors.     

Interfacial adsorption state of protonated lipophilic porphyrins in a liquid-liquid system by using reflection spectrometry.

Analysis by reflection spectrometry was performed to clarify the interfacial adsorption of protonated lipophilic tetraphenylporphyrin derivatives in a dodecane-aqueous sulfuric acid system, and to confirm the utility of partial reflection spectroscopy. Interfacial adsorption was not observed for porphyrins substituted at the 2,6 positions of meso-phenyl groups, suggesting that the substituents prevent porphyrins from forming aggregates by steric hindrance. Polymorphous J-aggregates of acid dications were produced by tetra-p-tolylporphyrin with a saturated interfacial molecular density of 1.0 x 10(-10) mol cm(-2), which could yield 48 degrees as a mean tilting angle of the pyrrole ring plane from the interface normal. Partial-reflection spectrometry can provide sensitive detection and molecular orientation analysis of interfacial adsorbates.     

Photoemission study of the modification of the electronic structure of transition-metal overlayers on TiO2 surfaces II. Cr on TiO2(0 0 1)

The electronic states of the Cr overlayers on TiO₂(0 0 1) surfaces have been investigated using angle-resolved and resonant photoemission spectroscopy with synchrotron radiation. At lower coverages, Cr deposition on TiO₂(0 0 1) creates two well separated in-gap emissions due to the formation of surface Ti³⁺ (3d¹) ions and Cr³⁺ (3d³) ions. At higher coverages, the in-gap emission is developed into the 2-peak-structure emission of Cr 3d character. The corresponding state is considered to be of metallic nature from the viewpoint of the high ability of oxygen adsorption, but has no Fermi edge, indicating a possibility of forming small Cr clusters on TiO₂(0 0 1) at this stage.