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21.
Several transition metal salts were found to catalyze aza-Michael reactions of enones with carbamates efficiently. The catalytic activity was strongly dependent on the nature of the metal salts. While conventional Lewis acids such as BF(3).OEt(2), AlCl(3), or TiCl(4) showed lower activity, group 7-11 transition metal salts in higher oxidation states such as ReCl(5), Fe(ClO(4))(3).9H(2)O, RuCl(3).nH(2)O, OsCl(3).3H(2)O, RhCl(3).nH(2)O, PtCl(4).5H(2)O, or AuCl(3).H(2)O exhibited higher catalytic activity. [reaction: see text] 相似文献
22.
Ochiai M Suefuji T Miyamoto K Tada N Goto S Shiro M Sakamoto S Yamaguchi K 《Journal of the American Chemical Society》2003,125(3):769-773
Reported here for the first time are the synthesis and characterization of supramolecular complexes between diaryl-lambda(3)-iodanes and 18-crown-6 (18C6). Slow evaporation of solvents afforded 1:1 and 2:1 complexes between Ph(2)IBF(4) and 18C6 as stable crystals, depending on the conditions. X-ray crystal structures of these complexes indicated that each iodine atom contacts with the three adjacent oxygen atoms of 18C6 through two hypervalent secondary bonding and a weak interaction. (1)H NMR analyses and CSI-MS spectra showed that, in dichloromethane solution, Ph(2)IBF(4) exclusively forms the 1:1 complex with 18C6 (binding constant K(a), 1.02 x 10(3) M(-)(1)). The binding constants decrease with the increased solvent donor ability (Gutmann's DN). Changing the heteroatom ligand from BF(4) to the less nucleophilic PF(6) and AsF(6) increased the binding constant by about six times. Substitution of an electron-withdrawing group onto the para position of Ph(2)IBF(4) tends to increase in the complex stability. A linear Hammett relationship (rho = 0.59) between log K(a) and sigma(p)(+) values of substituents indicates that the diaryl-lambda(3)-iodanes with electropositive iodine(III) interact more efficiently with 18C6. Decreased binding magnitude was measured with 15C5, dibenzo-18C6, dibenzo-21C7, and dibenzo-30C10. 相似文献
23.
The reaction of the dianion of phenylsulfinylacetone with alkyl halides afforded beta-keto sulfoxides, which were first chlorinated with hexachloroethane and then treated successively with KH and t-BuLi to give carboxylic acids in three-steps in moderate overall yields from the alkyl halides. This procedure affords a good method for a synthesis of carboxylic acids from alkyl halides with three-carbon elongation. 相似文献
24.
Tanaka T Teramura K Arakaki K Funabiki T 《Chemical communications (Cambridge, England)》2002,(22):2742-2743
Photoassisted selective catalytic reduction of NO with ammonia (photo-SCR) at low temperature over irradiated TiO2 in a flow reactor was confirmed to proceed efficiently and the adsorbed ammonia reacted with NO under irradiation of TiO2. 相似文献
25.
Itsuki Shindachi Hiroshi Hanaki Ryo Sasai Tetsuya Shichi Tatsuto Yui Katsuhiko Takagi 《Research on Chemical Intermediates》2007,33(1-2):143-153
Diarylethene derivatives (DE) covalently bonded to silanol oxygens of layered silicate surfaces, i.e., magadiite (Mag), were synthesized and investigated for their photochromic behavior. The DE-Mag layered hybrids were found to undergo reversible color change by alternating UV and visible light irradiation. A more highly efficient, reproducible photochromic behavior was realized with DE-Mag than with a corresponding DE-Si possessing silyl substituents on DE in place of the Mag surface. Moreover, the present covalently bonded DE exhibited an improvement over DE hybrids incorporated in layered double hydroxide (LDH) clays, in which the repetitive photochromic behavior decreased during alternating irradiation, due to the accumulation of the photochemically inert parallel isomers of DE. 相似文献
26.
[structure: see text] The structure of gelsemoxonine, isolated from Gelsemium elegans Benth., was revised to be a novel oxindole alkaloid having an azetidine unit. A new alkaloid, 14,15-dihydroxygelsenicine, which was presumed to be a biosynthetic precursor of gelsemoxonine, was also isolated. 相似文献
27.
Sato H Tashiro K Shinmori H Osuka A Aida T 《Chemical communications (Cambridge, England)》2005,(18):2324-2326
Upon complexation with 4,4[prime or minute]-bipyridine, a cyclic dimer of a fused porphyrin zinc complex, having two pi-electronically coupled binding sites, shows a strong negative cooperativity in the second guest binding, to allow stepwise formation of 1 : 1 and 1 : 2 inclusion complexes. 相似文献
28.
Komatsu H Iwasawa N Citterio D Suzuki Y Kubota T Tokuno K Kitamura Y Oka K Suzuki K 《Journal of the American Chemical Society》2004,126(50):16353-16360
The role of intracellular magnesium ions is of high interest in the fields of pharmacology and cellular biology. To accomplish the dynamic and three-dimensional imaging of intracellular Mg2+, there is a strong desire for the development of optimized Mg2+ fluorescent probes. In this paper we describe the design, synthesis, and cellular application of the three novel Mg2+ fluorescent probes KMG-101, -103, and -104. The compounds of this series feature a charged beta-diketone as a binding site specific for Mg2+ and a fluorescein residue as the fluorophore that can be excited with an Ar+ laser such as is widely used in confocal scanning microscopy. This molecular design leads to an intensive off-on-type fluorescent response toward Mg2+ ions. The two fluorescent probes KMG-103 and -104 showed suitable dissociation constants (Kd,Mg2+ = 2 mM) and nearly a 10-fold fluorescence enhancement over the intracellular magnesium ion concentration range (0.1-6 mM), allowing high-contrast, sensitive, and selective Mg2+ measurements. For intracellular applications, the membrane-permeable probe KMG-104AM was synthesized and successfully incorporated into PC12 cells. Upon application of the mitochondria uncoupler FCCP to the probe-incorporated cells, the resulting increase in the free magnesium ion concentration could be followed over time. By using a confocal microscope, the intracellular 3D magnesium ion concentration distributions were satisfactorily observed. 相似文献
29.
The crystal structure of SrAl2O4 at 1073 K was determined from conventional X-ray powder diffraction data using direct methods, and it was further refined by the Rietveld method. The structure was hexagonal (space group P63, Z=6) with a=0.89260(3) nm, c=0.84985(2) nm and V=0.58639(3) nm3. Final reliability indices were Rwp=7.87%, Rp=5.87% and RB=4.19%. The [AlO4] tetrahedra are linked to form trigonally distorted rings and they are joined in layers. These layers are stacked with a two-layer repeat and connected by the tetrahedral apices. All of the Sr atoms occupy the centers of the rings when viewed along the c-axis. The structure is described as a stuffed derivative of tridymite. 相似文献
30.
Sasaki M Kawanishi E Nakai Y Matsumoto T Yamaguchi K Takeda K 《The Journal of organic chemistry》2003,68(24):9330-9339
Metalated O-silyl cyanohydrins of beta-silyl-alpha,beta-epoxyaldehyde have been found to serve as functionalized homoenolate equivalents by a tandem sequence involving base-promoted ring opening of the epoxide, Brook rearrangement, and alkylation of the resulting allylic anion. On the basis of mechanistic studies involving competitive experiments using the diastereomeric cyanohydrins, we propose a reaction pathway involving a silicate intermediate 36 formed by a concerted process via an anti-opening of the epoxide followed by the formation of an O-Si bond. 相似文献