Regioselective 1,4-addition of nucleophiles to 1,3-diene monoepoxides catalyzed by palladium complex

1,3-Diene monoepoxides react with nucleophiles in the presence of palladium complex as a catalyst under neutral conditions to give 1,4-adducts selectively. The 1,4-adducts are allylic alcohols and there is a possibility of another nucleophilic attack. Ester of Monarch butterfly pheromone was prepared.     

Marine sterols—IV : Structure and synthesis of amuresterol,a new marine sterol with unprecedented side chain,from Asterias amurensis lütken

Amuresterol, a new marine C₂₇ sterol, was isolated from an asteroid Asterias amurensis, and its structure was confirmed as biogenetically unprecedented 22-trans-27-nor-(24S)-24-methylcholesta-7, 22-dien-3β-ol (1) from the spectral data and by synthesis. Gas-liquid chromatography indicated that 1 is a common sterol in six species of asteroids collected in Hokkaido.     

Highly active, immobilized ruthenium catalysts for oxidation of alcohols to aldehydes and ketones. Preparation and use in both batch and flow systems

A novel, highly active immobilized ruthenium catalyst, which can be successfully used in oxidation of alcohols to aldehydes and ketones, has been developed. In contrast to most immobilized catalysts, the Ru catalyst has activity that is higher than that of the original non-immobilized catalyst. In a batch system, the Ru catalyst was recovered and reused several times without loss of activity. The catalyst was also applied to a flow system, in which excellent conversions and yields were demonstrated. No leaching of Ru was observed in both cases.     

Recognition of chiral catechols using oxo-titanium phthalocyanine

Oxo-titanium phthalocyanine (TiOPc) derivatives of catechin and hematoxylin (natural ortho-diol type chiral compounds) have been prepared and characterized by spectral and chromatographic techniques. It is demonstrated that the TiOPc unit is an excellent template for chiral recognition through its isolated Q-transitions. The formation of a helical dimeric complex with hematoxylin induces strong CD-activity in the Q-band region. Ab initio geometry optimizations were combined with a Kuhn-Kirkwood coupled-oscillator mechanism to obtain the absolute configuration of hematoxylin. In addition, it is shown that the described chiroptical recognition method is sensitive to slight conformational changes.     

Subincanadines A-C,novel quaternary indole alkaloids from Aspidosperma subincanum

Three novel quaternary indole alkaloids with an unprecedented 1-azoniatricyclo[4.3.3.0(1,5)]undecane moiety, subincanadines A-C (1-3), as well as two new indole alkaloids with a 1-azabicyclo[5.2.2]undecane moiety, subincanadines D (4) and E (5), and a new indole alkaloid with a 1-azabicyclo[4.3.1]decane moiety, subincanadine F (6), have been isolated from the barks of Aspidosperma subincanum Mart, and the structures of 1-6 and the stereochemistry of 1-3 were elucidated by spectroscopic data and chemical means.     

Synthetic studies on macrolactin A by using a (diene)Fe(CO)3 complex

The stereoselective synthesis of the two segments 3 and 4 of macrolactin A 1 is described. Macrolactin A is a 24-membered polyene macrolide antibiotic, which is of interest due to a strong activity against B16-F10 murine tumor cell and HIV-1 virus. The key step of the synthesis is the 1,2-migration reaction of a (diene)Fe(CO)₃ complex with a introduction of the thiol group to construct the unstable (E,Z)-conjugated dienic moiety (C8-C11).     

Detection of potential membrane receptor proteins concerning circadian rhythmic leaf movement of legumes using novel photoaffinity probe compounds

Circadian rhythmic plant leaf movement, called nyctinasty, is controlled by a time-course change in the internal concentration of the leaf-movement factor in the plant body. We report that specific binding protein (210 and 180 kDa) for a leaf-movement factor, potassium lespedezate, is contained in the plasma membrane of the plant motor cell. These proteins would be potential receptors for leaf-movement factor to control the leaf movement.     

Contrasteric stereochemical dictation of the cyclobutene ring-opening reaction by a vacant boron p orbital

Cyclobutene, having a pinacolatoboryl group at the 3-position, was prepared by the reaction of trimethyl borate with a cyclobutenyl anion, which was generated by reductive lithiation of 3-(phenylselenyl)cyclobutene. Its thermal ring-opening reaction provided (Z)-1-borylbuta-1,3-diene selectively despite the arising steric congestion. The contrasteric behavior was accounted for by assuming an electron-accepting interaction of the vacant boron p orbital with the distorted breaking sigma orbital in the inward transition state.     

Rational design of CH/pi interaction sites in a basic resolving agent

A novel synthetic basic resolving agent, cis-1-aminobenz[f]indan-2-ol (ABI), was rationally designed by introducing effective CH/pi interaction sites to cis-1-aminoindan-2-ol (AI), whose chiral recognition ability has been reported from our laboratory. ABI was applicable to a wide variety of racemic arylalkanoic acids and showed moderate to excellent chiral recognition ability, which was obviously higher than that of AI. The fundamental and important role of CH/pi interactions, such as tunable CH(sp(2))/pi and CH(sp(3))/pi interactions, in the chiral recognition by ABI was revealed by X-ray crystallographic study.