A new gluco indole alkaloid, 3, 4-dehydro-5-carboxystrictosidine, from Peruvian Uña de Gato (Uncaria tomentosa)

A new gluco indole alkaloid, 3,4-dehydro-5-carboxystrictosidine, was obtained from Peruvian U?a de Gato (Cat's Claw, original plant: Uncaria tomentosa) together with two known gluco indole alkaloids. This compound was the first example of isolation of a gluco monoterpenoid indole alkaloid having a 3,4-dihydro-beta-carboline ring system from nature. A characteristic feature of the compound was the quick replacement of the methylene hydrogens on C-14 with deuterium that was observed when it was dissolved in CD3OD. We demonstrated a similar proton-deuterium exchange on a model compound, 1-methyl-3,4-dihydro-gamma-carboline, in CD3OD solution.     

Phosphane Sulfide/Octacarbonyldicobalt-Catalyzed Pauson - Khand Reaction Under an Atmospheric Pressure of Carbon Monoxide

Convenient access to cyclopentenones is provided by catalytic intra- and intermolecular Pauson - Khand reactions in the presence of octacarbonyldicobalt and tributylphosphane sulfide (see scheme). In contrast to other reactions of this type, they proceed under mild conditions (70 degrees C, 1 atm CO), and commercially available [Co(2)(CO)(8)] can be used without further purification.     

Fatigue Crack Nucleation at Σ3(1 1 2) Boundary in a Ferritic Stainless Steel

The effect of a geometrical relationship between a grain boundary (GB) plane and a tensile axis on intergranular fatigue cracking along 3(1 1 2) twin boundaries has been investigated in Fe-30%Cr alloy crystals. Fatigue experiments were carried out on the three kinds of the specimens containing the 3(1 1 2) twin boundary. It was found that the fatigue cracking behavior was sensitive to the geometry of the GB plane. In a specimen where both the GB plane and a slip vector lying in the GB plane in adjacent grains are inclined to the tensile axis at 45°, the fatigue cracks were nucleated preferentially along the twin boundary at a stress amplitude of 170 MPa. The specimen with the GB plane normal to the tensile axis showed that the fatigue crack was initiated from a slip band formed within a constituent grain at a stress amplitude of 300 MPa. When the GB plane was inclined to the tensile axis but the slip vector lying in the GB plane was normal to the tensile axis, development of additional slips formed perpendicular to the GB plane were observed at a specific site of the GB. Initiation of intergranular fatigue cracks at the site was recognized at a stress amplitude of 250 MPa. It can be suggested that the GB plane normal to the tensile axis provides the highest fatigue performance among them. The difference in the cracking property among these specimens could be understood in terms of the effective Schmid factor derived from elastically incompatible stress.     

Molecular-level chiral discrimination and induction

The review describes the mechanism of chiral discrimination of racemic amines upon crystallization and the induction of chirality in organic reactions by using them as chiral auxiliaries. In order to form conglomerates, which can be resolved into the two enantiomers upon alternative seeding, both formation and packing of 2₁-columns are essentially very important. On the other hand, in order to achieve high efficiency in resolution through diastereomeric salt formation, which is the most practical method, one of a pair of diastereomeric salts derived from a racemic amine and an enantiomerically pure resolving agent should at least have two 2₁-columns and planar boundary surfaces in its crystal structure. On the basis of this knowledge, we developed several artificial chiral auxiliaries such as erythro-2-amino-1,2-diphenylethanol,cis-2-amino-1-acenaphthenol, andcis-2-amino-3,3-dimethyl-1-indanol. These were found to be very efficient chiral auxiliaries in asymmetric inductions: alkylation of chiral imines, catalytic borane-reduction, and alkylation of chiral N-acylated oxazolidinone.     

Cardiac glycosides: 5. Stereoselective syntheses of digitoxigenin α-D, β-D, α-L,and β-L-glucosides

As part of a continuing study of cardiac g1ycos1des,^1,2 stereoselective syntheses of the four possible glucosides of digitoxigenin were developed via the thermodynamically produced tetra-O-benzyl-D- and L-glucosyl α-trichloroacetaimidates 2α and 11α, and the kinetically produced β-trichloroacetaimidates 2β and 11β. A 58%:19% isolated yield ratio of α-D and β-D benzyl protected glycosides 6 and 3 could be obtained in 30 minutes reaction at ?10°. Halide ion catalysis with a 2:1 excess of tetra-O-benzyl-α-D-glucopyranosyl bromide for 14 days in methylene chloride at room temperature gave a 39%:11% ratio of 6 and 3, along with 43% of recovered digitoxigenin. Debenzylation of the D-glucosides required milder conditions (20% Pd/C, atmospheric pressure, 45 min-1 hr) than the L-glucosides (40% Pd/C, 2 hr) but yields were typically 80% for both groups.     

Scattering of light by deformed disordered spherulites

The change in the light-scattering patterns upon deforming two-dimensional disordered spherulites is shown to arise from four effects occurring upon stretching: (1) the change in shape of the spherulite, (2) the change in average orientation of the optic axes of the scattering volume elements, (3) the change in deviation of the optic axis orientation angle from its average value, and (4) the change in the distance over which this deviation is correlated. The effects of these contributions upon the experimental scattering patterns are analyzed.     

A novel type secoiridoid glucoside,hydrangenoside a from Hydrangea macrophylla

Hydrangenoside A, isolated along with its three congeners from Hydrangea macrophylla, was proved to have a novel type of structure which is thought to be biosynthesized through an aldol-type condensation of secologanin with a unit formed by the shikimate-malonate route followed by decarboxylation.