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131.
Retro-allylation of homoallyl alcohol by rhodium catalysis occurs to generate allylrhodium species. This allylrhodium reacts with aldehydes to give the corresponding secondary alcohols in situ. Isomerization of these alcohols proceeds in the same pots to furnish the corresponding saturated ketones in good yields. [reaction: see text] 相似文献
132.
The modification of CaCO(3) crystal growth by synthetic L-Ser(PO(3)H(2)) and L-Thr(PO(3)H(2)) containing polypeptides is described. The amino acids Gly, L-Glu, L-Asp, L-Ser, L-Ala, and L-Lys induced rhombohedral calcite with a rough surface. Dipeptides, Xaa-L-Ser(PO(3)H(2)) (Xaa = Gly, L-Glu, L-Asp, L-Ser, L-Ala and L-Lys) induced vaterite crystals in the lower [Ca(2+)]. On the other hand, L-Ser(PO(3)H(2))-containing polypeptides formed spherical vaterite and fibrous calcite. The characteristic helical calcite was found in the presence of copoly[L-Ser(PO(3)H(2))(75)L-Asp(25)] or poly[L-Ser(PO(3)H(2))(3)-L-Asp]. Fibrous calcite, spherical vaterite, and helical calcite crystals were subjected to XRD and EDX analysis. XRD revealed the specific faces of these crystals. EDX spectra and surface analysis visualized the localization of the polypeptides and CaCO(3) components. Together with TEM and SAED data, we propose hypothetical growth mechanisms for the fibrous and helical calcite crystals. 相似文献
133.
134.
Haruka Egawa OoyamaAkiko Hayashi Toshiki MamuraTakashi Ide Toshihiko HinoTakuya Tanigami Katsuhira Yoshida 《Journal of photochemistry and photobiology. A, Chemistry》2012,230(1):38-46
Structural isomers of unsymmetric polycyclicphenazine-type D-π-A fluorescent dyes have been newly synthesized and characterized in both solution and polymer films. The dyes exhibited two strong absorption bands at around 328-401 nm and 516-532 nm, and an intense fluorescence band at around 595-629 nm (Φ = 0.32-0.84) in 1,4-dioxane. The dye-doped polymer films showed good ability of wavelength conversion; the films can efficiently convert ultraviolet and green-yellow lights into red light (Φ = 0.43-0.86). Moreover, the photostability of the dyes-doped PS, PMMA, and PLA films has been investigated. 相似文献
135.
Amphiphilic copolymers using hydrophilic N,N‐dimethylacrylamide (DMA), hydrophobic methyl methacrylate (MMA) and a crosslinkable monomer, 3‐methacryloyloxypropyl trimethoxysilane (MTSi), were synthesized and evaluated as coating materials for leukocyte removal filters for whole blood. When filters composed of non‐woven fabrics were coated with crosslinked synthesized copolymers, the elution ratios of the copolymers to water were adequately low because of the crosslinking with trimethoxysilane groups of MTSi units in the copolymers. Filters coated with crosslinked poly(DMA‐co‐MTSi) having a 0.96 mole fraction of DMA units showed a 0.35 ± 0.44% platelet permeation ratio and a logarithmic reduction of 4.0 ± 0.68 for leukocytes. On the other hand, an increase in the content of MMA units in the DMA‐containing copolymers improved the permeation ratio of the platelets dramatically. Filters coated with crosslinked poly(DMA‐co‐MMA‐co‐MTSi) containing a 0.39 mole fraction of MMA units and a 0.58 mole fraction of DMA units showed an 86 ± 3.0% platelet permeation ratio and a logarithmic reduction of 2.1 ± 1.2 for leukocytes. This indicates that an adequate content of hydrophobic monomer units, such as MMA units, is necessary for effective platelet permeation. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
136.
Shoji M Imai H Shiina I Kakeya H Osada H Hayashi Y 《The Journal of organic chemistry》2004,69(5):1548-1556
An oxidative dimerization reaction, involving the three successive steps of oxidation, 6 pi-electrocyclization, and Diels-Alder reaction, has been experimentally and theoretically investigated for the three 2-alkenyl-3-hydroxymethyl-2-cyclohexen-1-one derivatives epoxyquinol 3, epoxyquinone 6, and cyclohexenone 10. Of the sixteen possible modes of the oxidation/6 pi-electrocylization/Diels-Alder reaction cascade for the epoxyquinone 6, and eight for the cyclohexenone 10, only the endo-anti(epoxide)-anti(Me)-hetero and endo-anti(Me)-hetero modes are, respectively, observed, while both endo-anti(epoxide)-anti(Me)-hetero and exo-anti(epoxide)-anti(Me)-homo reaction modes occur with the epoxyquinol 3. Intermolecular hydrogen-bonding is found to be the key cause of formation of both epoxyquinols A and B with 3, although epoxyquinone 6 and cyclohexenone 10 both gave selectively only the epoxyquinol A-type product. In the dimerization of epoxyquinol 3, two monomer 2H-pyrans 5 interact with each other to afford intermediate complex 28 or 29 stabilized by hydrogen-bonding, from which Diels-Alder reaction proceeds. Theoretical calculations have also revealed the differences in the reaction profiles of epoxyquinone 6 and cyclohexenone 10. Namely, the rate-determining step of the former is the Diels-Alder reaction, while that of the latter is the 6 pi-electrocyclization. 相似文献
137.
The reaction of Mn(III) salen-type complexes with di- and tetraanionic α-Keggin-type polyoxometalates (POMs) was performed, and three types of Coulombic aggregations containing Mn(III) out-of-plane dimeric units (abbreviated as [Mn(2)](2+)) that are potentially single-molecule magnets (SMMs) with an S(T) = 4 ground state were synthesized: [Mn(2)(5-MeOsaltmen)(2)(acetone)(2)][SW(12)O(40)] (1), [Mn(2)(salen)(2)(H(2)O)(2)](2)[SiW(12)O(40)] (2), and [Mn(5-Brsaltmen)(H(2)O)(acetone)](2)[{Mn(2)(5-Brsaltmen)(2)}(SiW(12)O(40))] (3), where 5-Rsaltmen(2-) = N,N'-(1,1,2,2-tetramethylethylene)bis(5-R-salicylideneiminate) with R = MeO (methoxy), Br (bromo) and salen(2-) = N,N'-ethylenebis(salicylideneiminate). Compound 1 with a dianionic POM, [SW(12)O(40)](2-), is composed of a 1:1 aggregating set of [Mn(2)](2+)/POM, and 2, with a tetraanionic POM, [SiW(12)O(40)](4-), is a 2:1 set. Compound 3 with [SiW(12)O(40)](4-) forms a unique 1D coordinating chain with a [-{Mn(2)}-POM-](2-) repeating unit, for which a hydrogen-bonded dimeric unit ([Mn(5-Brsaltmen)(H(2)O)(acetone)](2)(2+)) is present as a countercation. Independent of the formula ratio of [Mn(2)](2+)/POM, Mn(III) dimers and POM units in 1-3 form respective segregated columns along a direction of the unit cell, which make an alternate packing to separate evenly identical species in a crystal. The nearest intermolecular Mn···Mn distance is found in the order 2 < 3 < 1. The segregation of the [Mn(2)](2+) dimer resulted in interdimer distances long enough to effectively reduce the intermolecular magnetic interaction, in particular in 1 and 3. Consequently, an intrinsic property, SMM behavior, of Mn(III) dimers has been characterized in this system, even though the interdimer interactions are still crucial in the case of 2, where a long-range magnetic order competitively affects slow relaxation of the magnetization at low ac frequencies. 相似文献
138.
Efficient monocyclic 1,2-diazepine formation via a tandem electrocyclization reaction of cyclobutenones with lithiodiazoacetate is demonstrated. The reaction proceeds through an oxy anion-accelerated 4π-ring opening of cyclobutene followed by an 8π-ring closure of the resultant oxy anion-substituted diazo-diene under mild conditions to furnish a 1,2-diazepine via formal diazomethylene insertion into the C-C bond of cyclobutenone. 相似文献
139.
Nakanishi W Nakamoto T Hayashi S Sasamori T Tokitoh N 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(1):255-268
To clarify the nature of five-center, six-electron (5c-6e) C(2)Z(2)O interactions, atoms-in-molecules (AIM) analysis has been applied to an anthraquinone, 1,8-(MeZ)(2)ATQ (1 (Z=Se), 2 (Z=S), and 3 (Z=O)), and a 9-methoxyanthracene system, 9-MeO-1,8-(MeZ)(2)ATC (4 (Z=Se), 5 (Z=S), and 6 (Z=O)), as well as 1-(MeZ)ATQ (7 (Z=Se), 8 (Z=S), and 9 (Z=O)) and 9-MeO-1-(MeZ)ATC (10 (Z=Se), 11 (Z=S), and 12 (Z=O)). The total electronic energy density (H(b)(r(c))) at the bond critical points (BCPs), an appropriate index for weak interactions, has been examined for 5c-6e C(2)Z(2)O and 3c-4e CZO interactions of the n(p)(O)sigma*(Z--C) type in 1-12. Some hydrogen-bonded adducts were also re-examined for convenience of comparison. The total electronic energy densities varied in the following order: OO (3: H(b)(r(c))=0.0028 au)=OO (6: 0.0028 au)>OO (9: 0.0025 au)> or =NNHF (0.0024 au)> or =OO (12: 0.0023 au)>H(2)OHOH (0.0015 au)>SO (8: 0.0013 au)=SO (2: 0.0013 au)> or =SO (11: 0.0012 au)=SO (5: 0.0012 au)>HFHF (0.0008 au)=SeO (10: 0.0008 au)=SeO (4: 0.0008 au)> or =SeO (1: 0.0007 au)> or =SeO (7: 0.0006 au)>HCNHF (-0.0013 au). H(b)(r(c)) values for SO were predicted to be smaller than the hydrogen bond of H(2)OHOH and H(b)(r(c)) values for SeO are very close to or slightly smaller than that for HFHF in both the ATQ and 9-MeOATC systems. In the case of Z=Se and S, H(b)(r(c)) values for 5c-6e C(2)Z(2)O interactions are essentially equal to those for 3c-4e CZO if Z is the same. The results demonstrate that two n(p)(O)sigma*(Z--C) 3c-4e interactions effectively connect through the central n(p)(O) orbital to form the extended hypervalent 5c-6e system of the sigma*(C--Z)n(p)(O)sigma*(Z--C) type for Z=Se and S in both systems. Natural bond orbital (NBO) analysis revealed that n(s)(O) also contributes to some extent. The electron charge densities at the BCPs, NBO analysis, and the total energies calculated for 1-12, together with the structural changes in the PhSe derivatives, support the above discussion. 相似文献
140.
Construction of carbocyclic ring of indoles using ruthenium-catalyzed ring-closing olefin metathesis
The selective synthesis of substituted indoles was achieved by the ring-closing olefin metathesis (RCM)/elimination sequence or the RCM/tautomerization sequence of functionalized pyrrole precursors. The RCM/elimination sequence was also applied to double ring closure to yield a substituted carbazole. 相似文献