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. 相似文献
[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. 相似文献
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. 相似文献
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.
The structural parameters of α- and β-CdUO4 crystals are determined by X-ray powder diffraction technique. α-CdUO4 is rhombohedral and cell parameters are a = 6.233(3) Å and α = 36.12(5)°. β-CdUO4 crystallizes in a C-centered orthorhombic cell with a = 7.023(4), b = 6.849(3), c = 3.514 (2) Å. The space groups are for α-CdUO4 and Cmmm for β-CdUO4. α-CdUO4: 1U in (000), 1Cd in (), 2O(1) in ±(uuu), 2O(2) in ±(vvv); u = 0.113, v = 0.350, Z = 1. β-CdUO4: 2U in (), 2Cd in (), 4O(1) in (), 4O(2) in (); x = 0.159, y = 0.278, Z = 2. β-CdUO4 contains collinear uranyl UO2+2 groups with a UO(1) distance of 1.91 Å, located either along or parallel to the c axis whereas the UO(1) bond length in α-CdUO4 is 1.98 Å which is longer than the usual uranyl bond length. 相似文献
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. 相似文献
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
22–
, V
2–
and V
20
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
20
and V
22–
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
20
) and 21 meV (V
22–
). The appearance of a shallow level for V
20
can not be explained by a conventional Rydberg state model. The lifetime (290–300 ps) in V
20
is nearly constant in the temperature range from 10 to 300 K, while that in V
22–
increases from 260 ps at 10 K to 320 ps at 300 K. The lifetime (260 ps) in V
22–
is shorter than that in V
20
at low temperature, which is due to the excess electron density in V
22–
. At high temperature, however, the longer lifetime of V
22–
than that of V
20
is attributed to lattice relaxation around V
22–
. 相似文献