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81.
The reaction of the alpha-carbanion of p-tolyl 2-(trimethylsilyl)ethyl sulfoxide with esters followed by reduction with DIBAL gave alpha-(trimethylsilyl)methyl-beta-hydroxysulfoxides with high stereoselectivity. The stereoselective reaction was demonstrated to proceed through a dynamic kinetic resolution pathway via a six-membered cyclic transition state involving Si-O interaction. These reactions provide a convenient route for the synthesis of optically pure allylic alcohols. 相似文献
82.
Kadokawa J Kaneko Y Nagase S Takahashi T Tagaya H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(15):3321-3326
In this paper, we describe a new polymerization manner termed as "vine-twining polymerization" to produce amylose-polymer inclusion complexes. The polymerization was achieved by an enzymatic polymerization of alpha-D-glucose-1-phosphate monomer catalyzed by phosphorylase in the presence of polyTHF as a guest polymer. The structure of the product was determined by X-ray powder diffraction and (1)H NMR measurements to be the inclusion complex. The formation process of the inclusion complexes during the polymerization was also evaluated. Furthermore, the formation of the inclusion complexes by this polymerization method by using polyTHFs with various M(n)s and end groups, as well as other polyethers as the guest polymers, was examined. 相似文献
83.
The representative examples of beneficial effects of hydrophilic groups in aqueous organic reactions are described, including the Diels-Alder reactions, hetero Diels-Alder reactions, Claisen rearrangement, radical reactions, and transition metal-catalyzed reactions. Although the low solubility of organic molecules in water has been a bane in aqueous organic reactions, the incorporation of hydrophilic groups into the substrate structure can overcome the solubility problem and at the same time enhance the hydrophobic effect. In some cases, interesting micellar effects are observed because of the amphiphilic natures of such molecules. The emerging concept of "removable hydrophilic group," in which the solubility problems have been alleviated, yet the initial product can still be transformed into a variety of products with the removal of the hydrophilic groups, is also described. 相似文献
84.
Catalytic asymmetric synthesis of a nitrogen analogue of dialkyl tartrate by direct mannich reaction under phase-transfer conditions 总被引:1,自引:0,他引:1
[reaction: see text] Phase-transfer-catalyzed direct Mannich reaction of glycinate Schiff base 3 with alpha-imino ester 4 has been accomplished with high enantioselectivity by the utilization of N-spiro C(2)-symmetric chiral quaternary ammonium bromide 2 as a catalyst. This methodology enables the catalytic asymmetric synthesis of differentially protected 3-aminoaspartate, a nitrogen analogue of dialkyl tartrate. The product (syn-5) was converted into a precursor (6) of streptolidine lactam. 相似文献
85.
Uricase (UOx) and polyelectrolyte were used for preparation of a permselective multilayer film and enzyme multilayer films on a platinum (Pt) electrode, allowing the detection of uric acid amperometrically. The polyelectrolyte multilayer (PEM) film composed of poly(allylamine) (PAA) and poly(vinyl sulfate) (PVS) were prepared via layer-by-layer assembly on the electrode, functioning as H2O2-selective film. After deposition of the permselective film (PAA/PVS)2PAA, UOx and PAA were deposited via layer-by-layer sequential deposition up to 10 UOx layers to prepare amperometric sensors for uric acid. Current response to uric acid was recorded at +0.6 V vs. Ag/AgCl to detect H2O2 produced from the enzyme reaction. The response current increased with increasing the number of UOx layers. Even in the presence of ascorbic acid, uric acid can be detected over the concentration range 10−6-10−3 M. The response current and deposited amount of UOx were affected by deposition bath pH and the addition of salt. The deposition of PAA/UOx film prepared in 2 mg ml−1 solution (pH 11) of PAA with NaCl (8 mg ml−1) and 0.1 mg ml−1 solution (pH 8.5) of UOx with borate (100 mM) resulted in an electrode which shows the largest response to uric acid. The response of the sensor to uric acid was decreased by 40% from the original activity after 30 days. 相似文献
86.
In this article we describe a new method of polymerization called "vine-twining polymerization" for preparation of well-defined supramolecules, which are amylose-polymer inclusion complexes. The method was achieved by enzymatic polymerization of alpha-D-glucose-1-phosphate catalyzed by phosphorylase in the presence of various synthetic polymers such as polyethers, polyesters, poly(ester-ether), and amphiphilic block copolymer. Powder X-ray diffraction (XRD) and 1H-NMR measurements determined the structures of the products to be inclusion complexes. The XRD patterns were completely different from those of amylose and guest polymers. The 1H-NMR spectra of the products indicated that the structures were composed of amylose and guest polymers. The formation process of the inclusion complexes during the enzymatic polymerization was also evaluated. In addition, we revealed that the bulkiness of the end groups and the hydrophobicity of the guest polymers strongly affected the formation of the inclusion complexes. By means of this method of polymerization, a graft polymer having inclusion complexes as side chains was prepared. Furthermore, as an evolution of the "vine-twining polymerization," we attempted a system of parallel polymerization to form an inclusion complex of amylose with a strongly hydrophobic guest polymer. 相似文献
87.
Yamago S Ray B Iida K Yoshida J Tada T Yoshizawa K Kwak Y Goto A Fukuda T 《Journal of the American Chemical Society》2004,126(43):13908-13909
A new versatile method for conducting living radical polymerization has been developed in which organostibines induce consecutive group-transfer radical reactions with alkenes. The method has been successfully applied, for the first time, to the controlled polymerization of both conjugated and unconjugated vinyl monomers, and the desired polymers with predetermined molecular weight and low polydispersity index were obtained in excellent yields. This characteristic feature of this method is exemplified in the first synthesis of block copolymers composed of conjugated and unconjugated monomers, which would be of great importance as functional smart organic nanomaterials. 相似文献
88.
Hideyuki Tagaya Shigemitsu Sato Noriyuki Kuramoto Jun-Ichi Kadokawa Masa Karasu Koji Chiba 《Journal of inclusion phenomena and macrocyclic chemistry》1994,18(2):193-204
Weak bases such as 2-aminopyridine, 4-aminopyridine,o-phenylenediamine,p-phenylenediamine and aniline were intercalated into aluminium dihydrogentriphosphate (ADHP) using ultrasonic wave irradiation. The interlayer spacing of ADHP increased from 8.1 Å to 12.4–20.0 Å. From the values of the layer expansions and host/guest ratios, bilayer or monolayer structures were considered. Chemical oxidation of the aniline resulted in the formation of polyaniline in the ADHP layers.Author for correspondence. 相似文献
89.
Yoshiro Nishimura Akira Minamida Jun-Ichi Matsumoto 《Journal of heterocyclic chemistry》1988,25(2):479-485
A synthesis of 1,4-oxazine and pyrazine ring systems by an intramolecular cyclization of 7-substituted 1-ethyl-6-fluoro-1,4-dihydro-4-oxo-1,8-naphthyridine and -quinoline derivatives having a nitrogen or oxygen nucleophilic site in the C-7 appendage was studied. The in vitro antibacterial activities of compounds prepared by this method were tested. 相似文献
90.
Layered thin films composed of avidin and 2-iminobiotin-labeled poly(ethyleneimine) (ib-PEI) were prepared by a layer-by-layer deposition of avidin and ib-PEI on a solid surface, and the disintegration induced by changing environmental pH and adding biotin in the solution was studied. The avidin/ib-PEI layered film could be deposited only from the solutions of pH 10-12. The film did not form in pH 9 or more acidic media because of a low affinity of protonated 2-iminobiotin residues in ib-PEI to avidin. The avidin/ib-PEI layered films were stable in pH 8-12 solutions, while in pH 5-7 media the film decomposed spontaneously as a result of the protonation to 2-iminobiotin residues in ib-PEI. The avidin/ib-PEI films were disintegrated also upon addition of biotin and analogues in the solution owing to the preferential binding of biotin or analogues to the binding site of avidin. The decomposition rate was arbitrarily controlled by changing the type of stimulant (biotin or analogues) and its concentration. The avidin/ib-PEI films were disintegrated rapidly by addition of 10(-)(5) M of biotin or desthiobiotin, while the rate was slower upon adding the same concentration of lipoic acid or 2-(4'-hydroxyphenylazo)benzoic acid. On the other hand, the film was fully decomposed within 1 min in the 10(-)(3) M lipoic acid or 2-(4'-hydroxyphenylazo)benzoic acid solution. Thus, the decomposition rate is highly dependent on the concentration of the stimulants. It was observed that the stimuli-induced decomposition of the films is slow at pH 12, in contrast to a rapid decomposition in pH 8 medium due to a low affinity of the protonated 2-iminobiotin to avidin. The present system may be useful for constructing stimuli-sensitive devices that can release drug or other functional molecules. 相似文献