Direct catalytic asymmetric Mannich-type reactions of isomerizable aliphatic imines: chemoselective enolate formation from a hydroxyketone by a Zn-catalyst

A direct catalytic asymmetric Mannich-type reaction of isomerizable aliphatic imines is described. A Et₂Zn/(S,S)-linked-BINOL complex was suitable for chemoselective enolate formation from a hydroxyketone in the presence of isomerizable aliphatic N-diphenylphosphinoyl imines. The reaction proceeds smoothly and β-alkyl-β-amino-α-hydroxyketones were obtained in good yield and high enantioselectivity (up to 99% ee), albeit in modest to low diastereoselectivity.     

Synthesis of two naturally occurring 3-methyl-2,5-dihydro-1-benzoxepin carboxylic acids

[structures: see text] Two naturally occurring 3-methyl-2,5-dihydro-1-benzoxepin carboxylic acids, 6-hydroxy-3-methyl-8-(phenylethyl)-2,5-dihydro-1-benzoxepin-9-carboxylic acid (radulanin E) (1) and 9-hydroxy-3-methyl-2,5-dihydro-1-benzoxepin-7-carboxylic acid (2), were synthesized using Stille coupling followed by Mitsunobu cyclization.     

Modification of silica gel with diethylamino group by novel reaction and its characterization

1,3,5,7-Tetramethylcyclotetrasiloxane (H₄) was deposited on silica gel at 80°C by utilizing a chemical vapor deposition (CVD) method, where it was catalytically polymerized to form a surface coating of polymethylsiloxane (PMS). Treated silica gel (PMS-Si) increased in weight up to a plateau level, and there was no further increase with increasing reaction time. The film of PMS was partially cross linked; typical values of crosslinking ratio and film thickness were 2% and 0.6 nm, respectively. An anionic ion exchanger containing diethylamino groups was synthesized from PMS-Si by hydrosilylation of allyl glycidyl ether followed by treatment with diethylamine. Its structure was confirmed by¹³C and²⁹Si CP/MAS NMR spectroscopy and FT-IR spectrophotometry. Characterization of silica gel (DEA-Si) modified with diethylamino group was evaluated by a packing of the column for liquid chromatography. As a mixture of five nucleotides was completely separated, it was recognized that DEA-Si was operated by ion exchange action. Because the surface of the silica gel was covered with hydrophobic PMS, the peak heights and retention times did not change after washing of the column with alkaline solution.     

Water‐Soluble N‐(n‐Fatty acyl)chitosans

Chitosan was partially N‐acylated by treatment with n‐fatty acid anhydrides in a homogeneous solution in 2 vol.‐% aqueous acetic acid‐methanol (1:2 v/v). The degree of substitution (d.s.) for N‐acyl groups in the water‐soluble N‐acylchitosan derivatives was in the range of 0.42–0.82 for N‐acetyl, 0.37–0.76 for N‐propionyl, 0.52–0.71 for N‐butyryl and 0.54–0.64 for N‐pentanoyl and ca. 0.58 for N‐hexanoyl, respectively.

Water soluble N‐(n‐fatty acyl)chitosans.     

Synthesis of pyrimidine derivatives using N-bis(methylthio)methylenecyanamide

N-Bis(methylthio)methylenecyanamide ( 1 ) was allowed to react with active methylene compounds (methyl cyanoacetate, dimethyl malonate, ethyl acetoacetate, ethyl phenylacetate) in the presence of potassium carbonate or potassium hydroxide in dimethyl sulfoxide followed by the treatment using appropriate a base or an acid to give the corresponding 6-methylthiouracil derivatives in 15–80% yields. These uracil derivatives are found to be useful intermediates for the synthesis of 6-aminouracils and fused pyrimidine derivatives.     

Orientation control of perovskite thin films on glass substrates by the application of a seed layer prepared from oxide nanosheets

Orientation control of perovskite compounds was investigated by the application of a seed layer prepared from oxide nanosheets. An aqueous suspension of oxide nanosheets was prepared by the exfoliation of a layered compound of KCa₂Nb₃O₁₀ oxide grains. A seed layer composed of (TBA)Ca₂Nb₃O₁₀ nanosheets (TBA = tetrabutylammonium) was formed on a glass substrate by simply dip coating it in the suspension. Two kinds of perovskite compounds, LaNiO₃ (LNO) and Pb(Zr,Ti)O₃ (PZT) with a preferred orientation of (00l) were successfully grown on this seeded glass substrate. In this study, the relation between lattice mismatch and electrical properties is investigated. A large, oriented PZT film with a size of 5 ×4 cm shows an improved P-E hysteresis behavior by use of this orientation control.     

Studies of divacancy in Si using positron lifetime measurement

The charge state dependence of positron lifetime and trapping at divacancy (V₂) in Si doped with phosphorus or boron has been studied after 15 McV electron irradiation up to a fluence of 8.0×10¹⁷ e/cm². The positron trapping cross sections for V ₂ ^2– , V ₂ ^– and V ₂ ⁰ at 300 K were about 6×10^–14, 3×10^–14 and 0.1–3×10^–14 cm², respectively. For V ₂ ⁺ , however, no positron trapping was observed. The marked difference in the cross sections comes from Coulomb interaction between the positron and the charged divacancy. The trapping rates for V ₂ ⁰ and V ₂ ^2– have been found to increase with decreasing temperature in the temperature range of 10–300 K. These results are well interpreted by a two-stage trapping model having shallow levels with energy of 9 meV (V ₂ ⁰ ) and 21 meV (V ₂ ^2– ). The appearance of a shallow level for V ₂ ⁰ can not be explained by a conventional Rydberg state model. The lifetime (290–300 ps) in V ₂ ⁰ is nearly constant in the temperature range from 10 to 300 K, while that in V ₂ ^2– increases from 260 ps at 10 K to 320 ps at 300 K. The lifetime (260 ps) in V ₂ ^2– is shorter than that in V ₂ ⁰ at low temperature, which is due to the excess electron density in V ₂ ^2– . At high temperature, however, the longer lifetime of V ₂ ^2– than that of V ₂ ⁰ is attributed to lattice relaxation around V ₂ ^2– .