New highly strained bridgehead imines, 2-azaadamant-1-ene and 4-azaprotoadamant-3-ene

An azaanalog of adamantene, 2-azaadamant-1-ene ($\text{1}$) and 4-azaprotoadamant-3-ene ($\text{7}$) were generated in the nonstatistical ratio via photolysis of 3-azidonoradamantane ($\text{2}$). The highly strained $\text{1}$ and $\text{7}$ could not be isolable but were trapped by MeOH. Acidolysis of $\text{2}$ was also reported, and discussed in comparison with the photolysis.     

Surface-enhanced Raman scattering from crystal violet adsorbed on a silver electrode

SERS from crystal violet (CV) on a Ag electrode was investigated under preresonance and resonance conditions. The excitation profile of the chemisorbed species is like that of dissolved molecules but intensities are ≈ 1000 times larger. The Raman enhancement is ≈ 10⁸ and exhibits a specific potential dependence even in the absence of adsorption-desorption process. At potentials where reduction of CV occurs leuco crystal violet was detected.     

Novel ring transformation reactions of xanthine derivatives

The novel ring transformation reactions were found in the reactions of 1,3,7,9-tetra-alkyl-8,9-dihydroxanthines and acetylenic compounds. The reaction of the dihydroxanthine with DMAD gave a propellane type compound and with methyl propiolate afforded the similar type compound and a pyrimido[4,5-b]diazepine derivative. The mechanism of these reactions was also discussed.     

Cyclic dithio-carbenium ion salts and their conversion to ketene dithioacetals

1,2-Ethanedithiol and 1,3-propanedithiol were treated with perchloric acid in acetic anhydride to give 2-methyl-1,3-dithiolan-2-yl and 2-methyl-1,3-dithian-2-yl perchlorates, respectively, which were converted to ketene dithioacetals by deprotonation with tertiary amines.     

Lignified natural products as potential medicinal resources. I. Potentiation of hemolytic plaque-forming cell production in mice

We have found that water-soluble extracts of lignified natural products are strong potentiaters of hemolytic plaque-forming cell production in mice. Apparently, the active components involved belong to a lignin family. Consequently, study of medicinal potential, especially immunopotentiating capacity, of lignified materials is important.     

A highly regio- and stereoselective synthesis of internal olefins via an elimination of trimethylstannyl group

Internal reaction of secondary alkyltin(IV) compounds having thionium ion gave internal trans olefins with high yield and regio- and stereoselectivity via 1,5- or 1,6-transfer of a hydride β to the trialkylstannyl group.     

Large-scale separation of metallic and semiconducting single-walled carbon nanotubes

In the applications of single-walled carbon nanotubes (SWNTs), it is extremely important to separate semiconducting and metallic SWNTs. Although several methods have been reported for the separation, only low yields have been achieved at great expense. We show a separation method involving a dispersion-centrifugation process in a tetrahydrofuran solution of amine, which makes metallic SWNTs highly concentrated to 87% in a simple way.     

A lithiation approach to cordycepin analogues variously substituted at the C-8 position

Several 8-substituted cordycepins were prepared via LDA lithiation of 2′,5′-bis-O-(t-butyldimethylsilyl)-cordycepin and successive reactions of its C-8 lithiated species with various types of electrophiles. Wittig reaction of the 8-formyl derivative was also examined.     

Chemo-enzymatic synthesis of 2′,3′-dideoxy-3′-fluoro-β-d-guanosine via 2,3-dideoxy-3-fluoro-α-d-ribose 1-phosphate

2,3-Dideoxy-3-fluoro-α-d-ribose 1-phosphate 2 was stereoselectively synthesized and converted to 2′,3′-dideoxy-3-fluoro-β-d-guanosine 1 by enzymatic reaction using purine nucleoside phosphorylase. This chemo-enzymatic strategy was first applied to the synthesis of 1.