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11.
Yoichi M.A Yamada 《Tetrahedron》2004,60(18):4087-4096
A novel catalyst PWAA, an assembled complex of phosphotungstic acid (H3PW12O40) and a non-cross-linked copolymer of N-isopropylacrylamide with an ammonium, was developed. It is an amphiphilic, cross-linked, and supramolecular insoluble complex and showed catalytic activity on oxidation with aqueous hydrogen peroxide. PWAA, used in 2.7×10−5-2.0×10−3 mol equiv., catalyzed oxidation of allylic alcohols, amines, and sulfides efficiently. The turnover number (TON) of PWAA reached up to 35,000. PWAA showed a good stability in organic/aqueous media and was reused three to five times.  相似文献   
12.
Control of viscoelasticity using redox reaction   总被引:1,自引:0,他引:1  
The viscoelasticity of a fluid was tuned with the Faradaic reaction of (11-ferrocenylundecyl)trimethylammonium bromide (FTMA), a "redox-switchable" surfactant. An aqueous solution of the reduced form of FTMA exhibited a remarkable viscoelasticity in the presence of sodium salicylate (NaSal) because of the formation of three-dimensional entanglement of wormlike micelles. Electrolytic oxidation of FTMA caused the viscosity of the system to dramatically decrease and the elasticity to disappear. This drastic decrease in viscoelasticity arose from the disruption of wormlike micelles. This novel electrorheological phenomenon is expected to be applicable to ink for inkjet printers, the electrochemically controlled release of substances entrapped in wormlike micelles of FTMA, and fluid flow rate control using electric signals.  相似文献   
13.
A highly selective ligand exchange reaction is realized in the self-assembled monolayer (SAM) of a triruthenium cluster on a gold electrode surface under precise electrochemical potential control. CO as well as NO molecules, which are known to play key roles in many chemical, biological, and environmental systems, can be efficiently introduced into the SAM by electrochemically tuning the electronic state of the Ru site. These unique surface reactions are more convenient and efficient than conventional ligand exchange reactions in solution and could be used for the elucidation of the electron-transfer mechanism in a biological system as well as in the development of molecular sensors and devices.  相似文献   
14.
The synthesis and properties of novel anthracene-bridged porphyrin dimers having an oxomolybdenum(V) porphyrin unit, H(2)(DPA)[Mo(V)O(OMe)] (1) and (DPA)[Mo(V)O(OMe)][Zn(II)(MeOH)] (2), and the relevant monomer porphyrin complexes Mo(V)O(MPP)OMe (3) and Zn(II)(MPP) (4) are presented. An oxomolybdenum(V) unit was introduced into one of the two porphyrins in DPA to give 1, which has a free-base porphyrin unit. By introducing a zinc(II) ion to the free-base part, a mixed-metal complex of 2 was prepared and isolated. The structure of 2 was analyzed by X-ray crystallography (2.(7)/(6)CH(2)Cl(2), triclinic, P(-)1 (no. 2), a = 15.2854(12) A, b = 19.9640(15) A, c = 13.6915(12) A, alpha = 90.968(3), beta = 113.108(4), gamma = 96.501(4), Z = 2, R1 = 9.9, wR2 = 19.2). The structure of 2 demonstrated that a methanol is stably coordinated to the Zn(II) ion with the aid of a hydrogen bond to the methoxo ligand on the Mo(V) ion in the binding pocket of DPA. The electrochemical measurements of 2 suggested that the methanol was kept in the pocket of DPA in solution even at the reduced state of the molybdenum ion.  相似文献   
15.
Yoichi M.A Yamada 《Tetrahedron》2004,60(18):4097-4105
The efficient heterogeneous Heck reaction was achieved by a new networked and supramolecular catalyst PdAS-V (1b). Employing of PdAS-V in 5.0×10−5 mol equiv. efficiently progressed the heterogeneous Heck reaction of a series of aryl iodides with acrylates, styrenes and acrylic acid. PdAS-V was successfully recycled five times without any decrease in its activity, and showed good stability in toluene and water, and hence the Heck reaction was efficiently performed in both reaction media. The use of 8.0×10−7 mol equiv. of PdAS-V resulted in the coupling product in 92% yield with the turnover number (TON) and the turnover frequency (TOF) of PdAS-V reached up to 1,150,000 and 12,000, respectively. The efficient synthesis of resveratrol was achieved via the PdAS-V-promoted Heck reaction.  相似文献   
16.
The crystal structure of C6H16N8O2·CuCl2, a biguanide metal complex, has been determined by X-ray diffraction data using MoK radiation. The compound crystallizes in the monoclinic space groupP21/a, witha=11.074(4),b=12.061(4),c=5.312(3)Å and=102.8(1)°.The structure was solved by direct methods and refined by full-matrix least-squares to a finalR value 0.037 with 1245 unique reflections. The complex molecule is centrosymmetric, with the Cu atom (0.5,0.5,0.5) on a crystallographic center of symmetry. The complex molecule is rhombic planar with a trans configuration.  相似文献   
17.
After immobilizing arylselenenyl bromide on polymer resin, the oxyselenenylation reaction of olefin was carried out in water. An amphiphilic polymer-supported arylselenenyl bromide was employed, and various intramolecular oxyselenenylation and deselenenylation reactions proceeded smoothly in water in fair chemical yields (up to an 83% yield).  相似文献   
18.
A novel MMP inhibitor, ageladine A (1) with antiangiogenic activity was isolated from a marine sponge Agelas nakamurai. Structure 1 was determined by a combination of spectroscopic and chemical methods to be an unprecedented structure of 4-(4,5-dibromo-1H-pyrrol-2-yl)]-1H-imidazo[4,5-c]pyridin-2-amine.  相似文献   
19.
Two novel palladium(0)-catalyzed cyclizations of allenenes are described. Treatment of allenenes such as N-(1-alkyl-2,3-butadienyl)-N-allylsulfonamide with an aryl halide and K(2)CO(3) in the presence of a catalytic amount of Pd(PPh(3))(4) in dioxane affords 2,3-cis-pyrrolidines in a stereoselective manner. In sharp contrast, cyclization of the same allenenes using catalytic Pd(2)(dba)(3) x CHCl(3) in the presence of allyl methyl carbonate in CH(3)CN leads to stereoselective formation of a 3-azabicyclo[3.1.0]hexane framework in moderate yields.  相似文献   
20.
Photoreactive polyamides having m- or 1 -type cyclobutane moiety were prepared via a topochemical photodimerization of 4-(3-oxo-3-phenyl-1-propenyl)benzoic derivatives,4 followed by polycondensation of cyclobutane dicarboxylate derivatives with diamines. From the spectral studies of resulted polyamides compared with the corresponding reference diamides, it was concluded that both types of polyamides were depolymerized photochemically to give the same type of amide derivative having chalcone moiety with a small amount of undefined side reaction. The cyclobutane ring of the m-dimer from 4-(3-oxo-3-phenyl-1-propenyl)benzoic acid in crystal is severely twisted presumably because of the enhanced steric repulsions between two pairs of adjacent substituents. The higher quantum yield of the m-dimer for the photocleavege, compared with that of the 1 -dimer, has been interpreted in terms of such steric repulsions by the strained structure of the m-dimer.  相似文献   
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