Chemical and isotopic compositions in acid residues from three meteorites

Chemical compositions of acid residues obtained from three types of meteorites, 1) Canyon Diablo (IA), 2) Allende (CV3) and 3) Nuevo Mercurio (H5) were determined. Refractory elements were generally enriched in these acid residues. The results match the features that acid residues contain primary condensates from the cooling solar gas as well as extra-solar grains. In the cases of Allende and Canyon Diablo, the contents of a series of refractory siderophile elements such as W, Re, Os, Ir, Mo, Ru and Pt were determined by INAA and AAS. Particularly, in acid residue of Allende, enrichment factors of these elements relative to CI are generally higher (7-20 times/CI), whereas in the cases of W and Mo, they are slightly depleted compared with those of Canyon Diablo. Since both elements would be the first metals to be oxidized under high oxygen fugacity, acid residue of Allende should contain fractions that were produced under oxidizing conditions. In these samples, the isotopic compositions of Ru have been measured by thermal ionization mass spectrometry. So far, in the measurements of acid residue of Allende, all Ru isotope ratios were found to be indistinguishable from terrestrial values within the experimental errors, though errors were large because of small Ru ion beam intensities

Structure-Activity Relationships of the Antitumor C5-Curcuminoid GO-Y030

1,5-Bis(4-hydroxy-3-methoxyphenyl)-1,4-pentadiene-3-one (2) was isolated from Curcuma domestica as a curcumin (1)-related compound, which we named C5-curcumin. Intrigued by the potent antitumor activity of C5-curcumin (2)-related 1,5-bisaryl-1,4-pentadiene-3-ones [bis(arylmethylidene)acetones, termed C5-curcuminoids], we previously conducted a structure–activity relationship study of C5-curcuminoids and showed that highly active GO-Y030 [1,5-bis(3,5-bis(methoxymethoxy)phenyl)-1,4-pentadiene-3-one (4)] is the most promising antitumor compound. In this study, a panel of C5-curcuminoids based on GO-Y030, consisting of 30 new and 10 known compounds, was synthesized to elucidate in detail which moiety of GO-Y030 is significant for antitumor activity. The results confirmed that both the cross-conjugated dienone moiety and the 3,5-bis(methoxymethoxy) substituent are important for the antitumor activity

Total Syntheses of Marrubiin and Related Labdane Diterpene Lactones

Total syntheses of the labdane diterpene lactones marrubiin, marrulibacetal, desertine, marrulibacetal A, marrubasch F, cyllenine C, marrulanic acid, and marrulactone are described. The trans-decalin moiety of these molecules was constructed in a stereoselective manner by a Pauson-Khand reaction, and the resultant cyclopentenone was oxidatively cleaved for formation of the lactone ring. Elongation of the side chain at C9 was achieved by an epoxide-opening reaction with a variety of nucleophiles, and the functional group manipulations completed the syntheses of these natural products. Stereochemistries of desertine could be established by the transformations

Stereoselective Synthesis of the CDE Ring System of Antitumor Saponin Scillascilloside E‑1

A stereoselective synthesis of the CDE ring portion of the antitumor saponin scillascilloside E-1 has been achieved, utilizing an Ireland–Claisen rearrangement to construct the contiguous tetrasubstituted stereocenters at C13 and C17 simultaneously and intramolecular nitrile oxide cycloaddition to form the five-membered ring as key steps

Synthesis of Chiral Building Blocks for Oxygenated Terpenoids through a Simultaneous and Stereocontrolled Construction of Contiguous Quaternary Stereocenters by an Ireland–Claisen Rearrangement

Methods for highly stereocontrolled syntheses of chiral building blocks with a triad of contiguous stereocenters, including two quaternary ones, have been developed. Ireland–Claisen rearrangement of the (<i>Z</i>)-silyl ketene acetal generated stereoselectively from the (<i>R</i>)-3-methylcyclohex-2-enyl ester derived from an acyclic carboxylic acid proceeded through a chairlike transition state to give the rearranged product with an <i>S</i> configuration at the position α to the carboxyl group. Introduction of a cyclic conformational constraint in the acid component completely switched the transition state of the rearrangement to a boatlike one, leading to the predominant formation of a product with an <i>R</i> configuration, from which pseudodiastereomeric α-hydroxy esters were obtained in a four-step sequence. The enyne obtained through a base-mediated double eliminative ring-opening reaction was successfully converted into advanced intermediates for the synthesis of 9-oxygenated labdane diterpenoids through a Heck reaction and a regioselective transformation of the resultant diene

Synthesis of Chiral Building Blocks for Oxygenated Terpenoids through a Simultaneous and Stereocontrolled Construction of Contiguous Quaternary Stereocenters by an Ireland–Claisen Rearrangement

Methods for highly stereocontrolled syntheses of chiral building blocks with a triad of contiguous stereocenters, including two quaternary ones, have been developed. Ireland–Claisen rearrangement of the (<i>Z</i>)-silyl ketene acetal generated stereoselectively from the (<i>R</i>)-3-methylcyclohex-2-enyl ester derived from an acyclic carboxylic acid proceeded through a chairlike transition state to give the rearranged product with an <i>S</i> configuration at the position α to the carboxyl group. Introduction of a cyclic conformational constraint in the acid component completely switched the transition state of the rearrangement to a boatlike one, leading to the predominant formation of a product with an <i>R</i> configuration, from which pseudodiastereomeric α-hydroxy esters were obtained in a four-step sequence. The enyne obtained through a base-mediated double eliminative ring-opening reaction was successfully converted into advanced intermediates for the synthesis of 9-oxygenated labdane diterpenoids through a Heck reaction and a regioselective transformation of the resultant diene