Complete replacement of H2 by D2 via Pd/C-catalyzed H/D exchange reaction

[reaction: see text] A general and in situ D2 gas generation method using 10% Pd/C-catalyzed H2-D2 exchange reaction in a H2-D2O system has been developed. H2 gas sealed in a reaction flask was efficiently converted into nearly pure D2 gas, which can be used for the reductive deuteration of substrates possessing reducible functionalities within the molecule.     

Stereochemistry and mechanism of catalytic hydrogenation of substituted cyclohexanones

Substituted alkylcyclohexanones were hydrogenated over several transition metal catalysts. The hydrogenation with freshly prepared Raney Ni gave predominantly the axial alcohols but catalyst to which sodium hydroxide was added or aged catalyst increased the stereoselectivity. In contrast to the PtO₂ hydrogenation in which the equatorial alcohols were favoured, more axial alcohols were obtained than the equatorial counterparts on Pt-black. On Pd catalyst the isomeric ratios of the cyclohexanols changed as the reaction progressed. This may be due to a decrease in the amount of hydrogen available caused by the strong adsorption of ketones on the catalyst. Rh catalyst gave more of the axial alcohols than any other catalyst used in the present study.     

Synthesis of the proposed structure of plakevulin A: revised structure of plakevulin A

A total synthesis of the proposed structure of plakevulin A was accomplished. However, the NMR spectral data of the synthetic plakevulin A were not identical of those of the reported compound. We next converted the synthetic plakevulin A into 1-dihydrountenone A. The ¹H and ¹³C NMR spectral data of 1-dihydrountenone A were identical with those of reported plakevulin A except for the peaks derived from levulinic acid. Thus, we repurified sample of the natural product and confirmed that the natural sample contained 1-dihydrountenone A and levulinic acid in the ratio of one to one. We also found that not plakevulin A but 1-dihydountenone A possessed the inhibitory activity against mammalian DNA polymerases α and β.     

Synthesis of Urea‐Tethered Disaccharides in Water

A new method for the synthesis of urea‐linked disaccharides in aqueous media has been developed. The key feature of our approach is two strained Steyermark‐type gluco‐ and galactopyranosyl oxazolidinones. Each oxazolidinone is attached to a pyranose ring in a di‐equatorial trans‐annulation framework. Reaction of these oxazolidinones with 4‐aminohexopyranose in water proceeded smoothly to afford the urea‐tethered cellobiose and lactose analogues. The galactose‐type oxazolidinone proved to be more reactive than the glucose‐type, which is explained by the presence of an axial hydroxy group at C4 in the former.     

A novel ring transformation of uracil into the benzene ring system

Reaction of 5-formyl-1,3-dimethyluracil with some active methylene compounds in the presence of base causes novel ring transformations to give the p-hydroxybenzoates and the nicotinate.     

Current-potential curves for facilitated ion transfer across oil/water interfaces in the presence of successive complex formation

A theoretical analysis of the current-potential curves for facilitated ion transfer across an oil/water interface is presented for the case where two complex species having an ion-to-ligand ratio of 1:1 and 1:2 are allowed to exist in the oil phase. Cyclic voltammograms are calculated numerically by using a finite difference method assuming that the ion transfer is reversible and the complex formation equilibria are maintained throughout the oil phase. When the ligand concentration in the oil phase is much smaller than the ion concentration in the aqueous phase and the former limits the ion-transfer current, two well separated peaks may develop even under the assumption of equilibrium conditions for the complex formation. The shape of the voltammogram is determined primarily by the ratio of the two reduced stability constants: b₁ = K₁^bc_L^O and b₂ = K₁K₂(^bc^O_L)², where K₁ and K₂ are the stability constants for 1:1 and 1:2 complexes in the oil phase and ^bc^O_L the ligand concentration in the bulk of the oil phase. The degree of peak separation thus depends not only on K₂/K₁ but also on ^bc^O_L. A method for estimating the two stability constants from the voltammograms is proposed.     

Prediction of measurement precision of apparatus using a chemometric tool in electrochemical detection of high-performance liquid chromatography

The relative standard deviation (RSD) of measurements in high-performance liquid chromatography with electrochemical detection (HPLC-ECD) was predicted by a chemometric tool based on the 1/f fluctuation model which is made up of white noise and a Markov process, called the Function of Mutual Information (FUMI) theory. FUMI theory can provide aprecise and reliable detection limit from a single measurement of noise and signal in HPLC-ECD. To obtain RSD (n = 5) for determination of (-)-epicatechin at five concentrations required 12.5 h, while the predicted RSD by FUMI theory required only 0.5 h (one measurement). Moreover, to trace the source of instrumental noise, power spectra of chromatographic baseline were used. Selection of a suitable apparatus in HPLC-ECD system, acquisition of RSD, and detection limits for determination of catechins by HPLC-ECD were simply and easily made by this chemometric tool within a very short time. The use of the FUMI theory for the prediction of measuring precision was more efficient and the optimization was less time-consuming to be suited for determination.     

Optimization of HPLC-ECD conditions for determination of catechins with precision and efficiency based on the FUMI theory.

A chemometric tool based on the Function of Mutual Information (FUMI) theory can provide a relative standard deviation (RSD) without repetitive measurements in high-performance liquid chromatography with electrochemical detection (HPLC-ECD). Two parameters: precision (= information content) phi and efficiency (= information content/time) theta, which were calculated from predicted RSD based on the FUMI theory, were used to optimize HPLC-ECD conditions, such as applied potential, flow rate, column length, and size of ODS porous packing. We selected catechins as analytes, and found that the most optimum applied potential and flow rate were +600 mV vs. SCE and 0.9 mL/min, respectively, because they gave the largest phi and theta values. Buffer concentration in mobile phase is less effective for giving large phi and theta values. Since the FUMI theory makes it possible to predict RSD without repetitive measurements, the present method saves considerable amounts of chemicals and experimental time, and was found to be useful for the optimization of experimental conditions for determination by HPLC-ECD.     

Synthesis of the enantiomers of cis-2-methyl-5-hexanolide,the major component of the sex pheromone of the carpenter bee

(2R,5S)-2-Methyl-5-hexanolide and its antipode were synthesized in highly optically pure state (?98–99% e.e.) starting from ethyl (S)-lactate and the enantiomers of methyl β-hydroxyisobutyrate. The specific rotations of our samples were [α]_D±91.0-93.5° (CHCl₃), while the reported values of the samples prepared by resolution or asymmetric synthesis were ±64.5–65.6°.