Conversion of optically active hydrindanone to (+)-bakkenolide-A

A total synthesis of (+)-bakkenolide-A was carried out via the key intermediate 4, which was prepared based on an asymmetric cyclization-carbonylation reaction established in our laboratory. Diastereoselective construction of the spirolactone moiety was achieved using Mitsuhashi's protocol as a key step.     

Mass spectrometry and photoelectron spectroscopy of o-, m-, and p-terphenyl cluster anions: the effect of molecular shape on molecular assembly and ion core character

Mass spectrometry and photoelectron spectroscopy of o-, m-, and p-terphenyl cluster anions, (o-TP)n(-) (n = 2-100), (m-TP)n(-) (n = 2-100), and (p-TP)n(-) (n = 1-100), respectively, are conducted to investigate the effect of molecular shape on the molecular aggregation form and the resultant ion core character of the clusters. For (o-TP)n(-) and (m-TP)n(-), neither magic numbers nor discernible isomers are observed throughout the size range. Furthermore, their vertical detachment energies (VDEs) increase up to large n and depend linearly on n(-1/3), implying that they possess a three-dimensional (3D), highly reorganized structure encompassing a monomeric anion core. For (p-TP)n(-), in contrast, prominent magic numbers of n = 5, 7, 10, 12, and 14 are observed, and the VDEs show pronounced irregular shifts below n = 10, while they remain constant above n = 14 (isomer A). These results can be rationalized with two-dimensional (2D) orderings of p-TP molecules and different types of 2D shell closure at n = 7 and 14, the monomeric and multimeric anion core, respectively. Above n = 16, the new feature (isomer B) starts to appear at the higher binding side of isomer A, and it becomes dominant with n, while isomer A gradually disappears for larger sizes. In contrast to isomer A, the VDEs of isomer B continuously increase with the cluster size. This characteristic size evolution suggests that the transition to modified 2D aggregation forms from 2D ones occurs at around n = 20.     

Reversible O-O bond cleavage and formation of a peroxo moiety of a peroxocarbonate ligand mediated by an iron(III) complex

A mononuclear iron(III) complex containing a peroxocarbonate ligand, [Fe(qn)2(O2C(O)O)]- (qn = quinaldinate), underwent the reversible O-O bond cleavage and reformation of the peroxo group via the formation of FeIV=O or FeV=O species, which was confirmed by the resonance Raman and ESI-TOF/MS measurements.     

anti-selective direct asymmetric Mannich reactions catalyzed by axially chiral amino sulfonamide as an organocatalyst

A direct asymmetric Mannich reaction using a novel axially chiral amino trifluoromethanesulfonamide (S)-3 has been developed in highly anti-selective and enantioselective manners. Thus, in the presence of a catalytic amount of (S)-3, the reactions between aldehydes and the alpha-imino ester 4 proceed smoothly to give the functional beta-amino aldehydes with significantly higher anti/syn ratio and enantioselectivity than previously possible.     

Diffusion and pair interactions of CO molecules on Pd(111)

The diffusion and interactions of CO molecules on Pd(111) were studied by scanning tunneling microscopy. By following the random walk motion of individual molecules as a function of temperature, an activation energy barrier for diffusion of 118 +/- 5 meV was determined. The interaction between CO molecules was found to be repulsive for pairs separated by one or two Pd(111) lattice distances, and weakly attractive at a separation of sqrt[3].     

Silver granules as an absorbent of halogens and oxides of sulphur

Summary A preparation of silver granules has been used as an absorbent for halogens and sulphur. Its absorptive capacities for halogens and for sulphur were determined at various temperatures. The capacities are favorably compared with that of electrolytic silver wool. Having a granular form, the material is more conveniently used than electrolytic silver wool, and is applicable to the determination of carbon-hydrogen, halogens, sulphur or oxygen.

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Zusammenfassung Gekörntes Silber wurde zur Absorption von Halogenen und Schwefel verwendet. Seine Absorptionskapazität für die genannten Elemente wurde bei verschiedenen Temperaturen bestimmt. Sie ist gleich gut wie die elektrolytisch gewonnener Silberwolle. Die körnige Form ist aber besser zu handhaben als Silberwolle und eignet sich für die Bestimmung von Kohlenstoff und Wasserstoff, der Halogene, des Schwefels und des Sauerstoffs.

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Résumé On a utilisé une préparation de grains d'argent comme absorbant des halogènes et du soufre. On a déterminé ses capacités d'absorption pour les halogènes et pour le soufre à températures variées. Le pouvoir absorbant subit une comparaison favorable avec celui de la laine d'argent électrolytique. En raison de la forme granulaire, l'utilisation est plus facile que celle de la laine d'argent électrolytique. On peut l'appliquer au dosage du carbone, d'hydrogène, des halogènes, du soufre ou de l'oxygène.

     

Monoamine oxidase inhibitors from Cinchonae Cortex

Three strong alkaloidal monoamine oxidase (MAO) inhibitors, quinine (1), cinchonicinol ([ 1S,3'R,4'R]-3-(3-ethenyl-4-piperidinyl)-1-(4-quinolinyl)-1-propanol) (2) and cinchonaminone ([ 3'R,4'S]-2-[2-(3-ethenyl-4-piperidinyl)-acetyl]-1H-indole-3-ethanol) (3), were isolated from Cinchonae Cortex (Cinchona succirubra Pav., Rubiaceae). The structures of 2 and 3 were elucidated on the bases of spectral data and chemical evidence, and 3 is a new alkaloid. The inhibitory effects on MAO of 1, 2, 3 and related alkaloids were assayed. The type of inhibition by 1 with respect to benzylamine as a substrate was competitive.