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81.
Rijssenbeek JT Saito T Malo S Azuma M Takano M Poeppelmeier KR 《Journal of the American Chemical Society》2005,127(2):675-681
The related parameters of cation size and valence that control the crystallization of Sr(3)CaRu(2)O(9) into a 1:2 B-site-ordered perovskite structure were explored by cationic substitution at the strontium and calcium sites and by the application of high pressure. At ambient pressures, Sr(3)MRu(2)O(9) stoichiometries yield multiphasic mixtures for M = Ni(2+), Mg(2+), and Y(3+), whereas pseudocubic perovskites result for M = Cu(2+) and Zn(2+). For A-site substitutions, an ordered perovskite structure results for Sr(3-x)Ca(x)CaRu(2)O(9), with 0 = x = 1.5. In contrast, Ba(2+) substitution for Sr(2+) is accompanied by a phase change to a hexagonal BaTiO(3) structure type. At high pressures and temperatures, a 1:2 B-site-ordered perovskite structure is stabilized for Sr(3-x)Ba(x)CaRu(2)O(9), with 0 = x = 3. The scarcity of B-site-ordered perovskite ruthenates at ambient pressure and the metastable nature of the high-pressure phases underscore the strict size and valence requirements that must be met by the constituent cations to achieve these uncommon ordered structures. 相似文献
82.
A unique asymmetric skeletal rearrangement of symmetrically alpha,alpha-disubstituted alpha-amino aldehydes has been accomplished for the first time using a chiral organoaluminum Lewis acid 1. For instance, treatment of (S)-2,2'-bis(trifluoromethanesulfonylamino)-1,1'-binaphthyl with Me3Al (1.0 equiv) in toluene at room temperature for 15 min and at 110 degrees C for an additional 15 min produced (S)-1, and a subsequent reaction with alpha -amino aldehyde 2a (R = CH2Ph) at -78 degrees C for 4 h and at -40 degrees C for 12 h resulted in the smooth rearrangement to the zwitterionic iminium intermediate A, which furnished the alpha-hydroxy ketone 3a (R = CH2Ph) in 93% isolated yield with 95% ee (S) after acidic hydrolysis. This result, together with other representative examples, clearly demonstrates the effectiveness of the present method for the hitherto difficult asymmetric synthesis of acyloins. Furthermore, we found that the treatment of the in situ generated A with DIBAH afforded the corresponding anti amino alcohol exclusively without loss of enantiomeric excess. Our approach casts light on the previously unexplored yet potential utility of alpha-amino aldehydes as synthetic building blocks and also provides a new entry to optically active alpha-hydroxy ketones and 1,2-amino alcohols. 相似文献
83.
Krishna Gopal Dongol M. Cristina Melo e Silva Kouki Matsubara Taisuke Matsumoto Shuntaro Mataka Thies Thiemann 《无机化学与普通化学杂志》2003,629(6):945-947
The preparation of two η6‐estra‐1, 3, 5(10), 6‐tetraene tricarbonylchromium complexes 4 and 6 are described. In both cases only one stereoisomer can be isolated, in contrast to other estrane‐tricarbonylchromium complexes, where complexations are non‐stereoselective. X‐ray crystal structural analysis of 4 discloses that only the more sterically hindered β‐facial isomer is formed. It is assumed that the 6, 7‐olefinic moiety exerts a directive influence on the complexation. 相似文献
84.
A synthesis of 1,2,5,6-tetrahydro-4H-benzo[3,4]cyclohepta[1,2-e]imidazo[1,2-c]pyrimidine (XII) having a novel ring system is described. Antidepressive activity of XII and its precursors VII-X was screened by inhibitory action of reserpine-induced hypothermia. 相似文献
85.
The structures of two new bitter triterpenes, ganoderic acid A and B. isolated from a mushroom Ganoderma lucidum (FR.) Karst. (Polyporaceae) were determined as 1 and 2 on the basis of spectral data. Ganoderic acid A is a novel highly oxidized triterpene bearing a boat-shaped A-ring of lanostane. 相似文献
86.
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
87.
Kakiuchi F Tsuchiya K Matsumoto M Mizushima E Chatani N 《Journal of the American Chemical Society》2004,126(40):12792-12793
Ruthenium-catalyzed silylation of sp3 C-H bonds at a benzylic position with hydrosilanes gave benzylsilanes. For this silylation reaction, Ru3(CO)12 complex showed high catalytic activity. This silylation proceeded at the methyl C-H bond selectively. For this silylation reaction, pyridyl and pyrazolyl groups, and the imino group in hydrazones, can function as a directing group. Several hydrosilanes involving triethyl-, dimethylphenyl-, tert-butyldimethyl-, and triphenylsilanes can be used as a silylating reagent. Coordination of an sp2 nitrogen atom to the ruthenium complex is important for achieving this silylation reaction. 相似文献
88.
89.
Ooi Y Hobara D Yamamoto M Kakiuchi T 《Langmuir : the ACS journal of surfaces and colloids》2005,21(24):11185-11189
In formation of binary self-assembled monolayers (SAMs) composed of 2-aminoethanethiol (AET) and 2-mercaptoethane sulfonic acid (MES) by adsorption from an ethanol solution on Au(111), the adsorption shows nearly ideal nonideality in that the surface ratio of MES to AET in the SAM is unity and does not depend on the mixing ratio of MES to AET in the bathing ethanol solution used for preparing SAMs, chi(soln)MES, over the wide range of chi(soln)MES between 0.01 and 0.95. X-ray photoelectron spectroscopy confirms that at least 80% of AET molecules adsorbed are protonated in this range of chi(soln)MES, indicating that the electrostatic interaction between positively charged AET and negatively charged MES is responsible to the observed nonideality. Correspondingly, there appears only one cathodic peak in a linear-sweep voltammogram of the reductive desorption of the SAM, having a narrow full width at half-maximum of about 20 mV. This suggests the presence of strong lateral attractive interaction between the adsorbed thiolates. 相似文献
90.
Zhi C Bando Y Tang C Xie R Sekiguchi T Golberg D 《Journal of the American Chemical Society》2005,127(46):15996-15997
We report for the first time that boron nitride nanotubes (BNNTs) may be dissolved in organic solvents by wrapping them with a polymer. Transmission electron microscopy and cathodoluminescence studies indicate the strong pi-pi interactions between BNNTs and the polymer. A band gap ranging from 5.2 to 5.5 eV was documented for the BNNTs independent of their geometrical characteristics by using ultraviolet-visible absorption experiments on composite films and thin BNNT films prepared from solutions. 相似文献