Dehydrogenative condensation of monohydrosilanes yielding disilanes in the presence of platinum complex catalysts

Dimethylphenylsilane was catalytically dehydrogenated and condensed in the presence of platinum complexes to give 1,1,2,2-tetramethyl-1,2-diphenyl-disilane.     

Oxidative addition of C-H bonds to RhCl(PMe3)3: relevant to the catalytic transformation of hydrocarbons

RhCl(PMe3)3 (1) reacts with benzene under irradiation to give the oxidative addition product, Rh(C6H5)(H)Cl(PMe3)3 (2). The reaction is promoted under CO2 atmosphere. The structure of 2 was fully characterized by X-ray crystallography as well as NMR, IR, and elemental analysis. The adduct (2) is unstable in solution even at room temperature to regenerate benzene and 1. The thermolysis of 2 under a CO atmosphere produces benzaldehyde along with the reductive elimination product, benzene. On the other hand, the prolonged photoreaction of 1 with benzene under CO2 resulted in the activation of the C-H bond and CO2 to yield Rh(C6H5)(eta2-CO3)(PMe3)3 (3).     

Multi-step application of immobilized reagents and scavengers: a total synthesis of epothilone C

The total synthesis of the cytotoxic antitumour natural product epothilone C has provided a stage for the exploitation and further development of immobilized reagent methods. A stereoselective convergent synthetic strategy was applied, incorporating polymer-supported reagents, catalysts, scavengers and catch-and-release techniques to avoid frequent aqueous work-up and chromatographic purification.     

Stability of phosphines under hydroformylation conditions

Phosphorus-carbon bonds of p-substituted triphenylphosphines were found to be cleaved under hydroformylation conditions in the presence of a rhodium, ruthenium, or cobalt carbonyl. Only p-isomers of the decomposition products (substituted benzaldehyde, benzyl alcohol, and/or biphenyl) were formed. The ability of metal carbonyls to cleave the PC bonds was Rh > Co > Ru. Tributylphosphine was stable under the conditions. The stability of metal carbonyl-phosphine catalyst systems was also examined and compared with the extent of PC bond cleavage.     

Diels-Alder reaction using a dendritic copper(II) triflate-catalyst: a positive dendritic effect on the chemical yield

A series of dendritic ligands with a 2,2′-bipyridine core was synthesized through the coupling of 4,4′-dihydroxy-2,2′-bipyridine with poly(arylether) dendron in fair yields. The corresponding copper(II) trifluoromethanesulfonate (triflate) dendrimers were applied as a Lewis acid catalyst to the Diels-Alder reaction. A positive dendritic effect on the chemical yields of adducts was observed.     

The conformational features of palytoxin in aqueous solution

Conformational features of palytoxin and acetylated palytoxin were investigated by detailed analyses of NOESY spectra. The conformational differences between palytoxin and acetylated palytoxin may account for the difference in the assembly state of palytoxin, which exists as an associated dimer, and the acetylated derivative, which exists as a monomer in aqueous solution. Two palytoxin units in the dimer may come in contact with each other at the hydrophobic region (C21-40) and the region around two conjugated double bonds (C60-84). The amino group of palytoxin is important for biological activities via Na/K ATPase, but it was not found to be involved in the contact faces of the two palytoxin units. This information should aid in revealing how palytoxin interacts with Na/K ATPase.     

Coordination complex between haemin and parallel-quadruplexed d(TTAGGG)

Haemin, iron(III)-protoporphyrin IX complex, and parallel-quadruplexed d(TTAGGG) have been shown to form a stable coordination complex which exhibits spectroscopic properties remarkably similar to those of haemoproteins.     

Subterranean electrical structure of Kozu-shima volcanic island, Japan

Following the electric current injection experiment carried out in 2009, a VLF-MT (Very Low Frequency Magnetotelluric) survey has been conducted in Kozu-shima Island to obtain further information on the subterranean electrical structure that might help understanding the results of our monitoring of geoelectric potentials. A number of VAN-type pre-seismic geoelectric potential anomalies were observed in 1997-2000, even showing a remarkable "Selectivity". However, similar pre-seismic anomalies were not observed during the Izu-Island volcano-seismic swarm 2000. All these observations would require extremely high degree of heterogeneity in the subterranean electrical structure of the volcanic island and its possible time changes. Several correlations between the results of this survey and the volcanic geology of the island and ground water distribution were found. Further investigation is needed for a complete explanation of the observed phenomena.     

Synthesis of Highly Emissive Fluorophores Based on Multiply Stacked Anthracene Arrangement

Newly designed fluorophore systems with feather-like structures were constructed by connecting bisanthracene building units via a concise reaction sequence of bromination, etherification, and desilylation. Spectroscopic characterizations revealed that all of the fluorophore systems achieved high light absorptivity and high emission efficiency by preventing closely spaced anthracene chromophores from mutual interactions to reduce concomitant energy loss by fluorescence quenching. The application of fluorophore systems for the preparation of light-harvesting dyad materials has successfully demonstrated their potential utility as versatile photofunctional tools.