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911.
The West Indian alcyonacean Pseudopterogorgia bipinnata (Verrill, 1864) is shown to contain a novel bisditerpenoid ether: biskallolide A (2). The structural assignment of 2 was mainly based on 1D and 2D NMR and MS spectral data and was further confirmed by synthesis. The 2-C-alkoxylation of furanopseudopteranes kallolide A (1) and isokallolide A (8) occurs spontaneously in some solvents and involves replacement of the C2 hydroxyl with an alkoxyl group to yield solvolysis products that display net retention of configuration. The facile solvolytic 2-C-acyloxylation of kallolide A was achieved readily under similar circumstances to afford kallolide A acetate (4) as the sole product. Mechanistic details in conversion of alcohols 1 and 8 into various solvolysis products, including dimeric ethers 2 and 9, were investigated in this study. Solvolysis of kallolide A and isokallolide A in [(18)O]-labeled solvent demonstrated that the C2 alkoxyl of the solvolysis products originated from the solvent, suggesting that these conversions may proceed through an S(N)1 mechanism with generation of a carbocation intermediate. The chemical structures of kallolide A derivatives 3-7and those of isokallolide A congeners 9-11 were established by detailed analysis of the spectral data. 相似文献
912.
Cabeza JA del Río I Fernández-Colinas JM García-Granda S Martínez-Méndez L Pérez-Carreño E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(24):6265-6278
The reactions of the triruthenium cluster complex [Ru3(mu-H)(mu3-eta2-HNNMe2)(CO)9] (1; H2NNMe2=1,1-dimethylhydrazine) with alkynes (PhC triple bond CPh, HC triple bond CH, MeO2CC triple bond CCO2Me, PhC triple bond CH, MeO2CC triple bond CH, HOMe2CC triple bond CH, 2-pyC triple bond CH) give trinuclear complexes containing edge-bridging and/or face-capping alkenyl ligands. Whereas the edge-bridged products are closed triangular species (three Ru-Ru bonds), the face-capped products are open derivatives (two Ru-Ru bonds). For terminal alkynes, products containing gem (RCCH2) and/or trans (RHCCH) alkenyl ligands have been identified in both edge-bridging and face-capping positions, except for the complex [Ru3(mu3-eta2-HNNMe2)(mu3-eta3-HCCH-2-py)(mu-CO)(CO)7], which has the two alkenyl H atoms in a cis arrangement. Under comparable reaction conditions (1:1 molar ratio, THF at reflux, time required for the consumption of complex 1), some reactions give a single product, but most give mixtures of isomers (not all the possible ones), which were separated. To determine the effect of the hydrazido ligand, the reactions of [Ru3(mu-H)(mu3-eta2-MeNNHMe)(CO)9] (2; HMeNNHMe=1,2-dimethylhydrazine) with PhC triple bond CPh, PhC triple bond CH, and HC triple bond CH were also studied. For edge-bridged alkenyl complexes, the Ru--Ru edge that is spanned by the alkenyl ligand depends on the position of the methyl groups on the hydrazido ligand. For face-capped alkenyl complexes, the relative orientation of the hydrazido and alkenyl ligands also depends on the position of the methyl groups on the hydrazido ligand. A kinetic analysis of the reaction of 1 with PhC[triple chemical bond]CPh revealed that the reaction follows an associative mechanism, which implies that incorporation of the alkyne in the cluster is rate-limiting and precedes the release of a CO ligand. X-ray diffraction, IR and NMR spectroscopy, and calculations of minimum-energy structures by DFT methods were used to characterize the products. A comparison of the absolute energies of isomeric compounds (obtained by DFT calculations) helped rationalize the experimental results. 相似文献
913.
Barluenga J Diéguez A Rodríguez F Fañanás FJ Sordo T Campomanes P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(19):5735-5741
The [W(CO)5]-catalyzed cycloisomerization reaction of 1,1-disubstituted 4-pentyn-1-ol derivatives has been studied from both, an experimental and theoretical point of view. Three different catalytic systems have been evaluated {preformed [(thf)W(CO)5], [W(CO)6]/excess Et3N, and [W(CO)6]/2 mol % Et3N]. We have found that the reaction proceeds to give the formal endo- or exo-cycloisomerization products depending on the amount of Et3N used and on the substitution along the alkyl chain of the starting alkynol. The theoretical study allowed us to find the mechanisms of the reactions which explain the formation of the formal endo- or exo-cycloisomerization products. 相似文献
914.
Hernández-Borges J Frías-García S Cifuentes A Rodríguez-Delgado MA 《Journal of separation science》2004,27(12):947-963
In this work, a critical and updated revision of the current situation of the analysis of pesticides by Capillary Electrophoresis (CE) is presented. The review has been written in two main sections. The first one presents a thorough revision of the various offline and on-line sample preconcentration procedures that have been used in conjunction with CE to analyze these compounds. The second part reviews the various detection strategies (i.e., UV, LIF, MS, and electrochemical) and CE modes that have been applied to the analysis of pesticides. Future trends that can be expected from this hot research area are also discussed. 相似文献
915.
Surface shear viscosity of food emulsifiers may contribute appreciably to the long-term stability of food dispersions (emulsions and foams). In this work we have analyzed the structural, topographical, and shear characteristics of a whey protein isolate (WPI) and monoglyceride (monopalmitin and monoolein) mixed films spread on the air-water interface at pH 7 and at 20 degrees C. The surface shear viscosity (etas) depend on the surface pressure and on the composition of the mixed film. The surface shear viscosity varies greatly with the surface pressure. In general, the greater the surface pressure, the greater are the values of etas. The values of etas for the mixed WPI-monoolein monolayer were more than one order of magnitude lower than those for a WPI-monopalmitin mixed film, especially at the higher surface pressures. At higher surface pressures, collapsed WPI residues may be displaced from the interface by monoglyceride molecules with important repercussions on the shear characteristics of the mixed films. A shear-induced change in the topography and a segregation between domains of the film forming components were also observed. The displacement of the WPI by the monoglycerides is facilitates under shear conditions, especially for WPI-monoolein mixed films. 相似文献
916.
Field-amplified sample stacking (FASS) leverages conductivity gradients between a volume of injected sample and the background buffer to increase sample concentration. A major challenge in applying FASS to on-chip assays is the initial setup of high-conductivity gradient boundaries in the region of the injected sample volume. We have designed, fabricated, and characterized a novel FASS-capillary electrophoresis (CE) chip design that uses a photoinitiated porous polymer structure to facilitate sample injection and flow control for high-gradient FASS. This polymer structure provides a region of high flow resistance that allows the electromigration of sample ions. We have demonstrated an electropherogram signal increase by a factor of 1100 in electrophoretic separations of fluorescein and Bodipy with, respectively, 2 microM and 1 microM initial concentrations. 相似文献
917.
A total synthesis of the marine alkaloid variolin B has been completed in 13 steps in an overall yield of 6.5% from 3-formyl-4-methoxypyridine. Our approach is based on the sequential formation of the 7-azaindole ring, the tricyclic pyrido[3',2':4,5]pyrrolo[1,2-c]pyrimidine ring system, and finally installation of the 2-aminopyrimidine ring at C5. The required 7-azaindole ring appropriately substituted is formed by a modified indole synthesis involving a nitrene insertion process (two steps). Formation of the annelated pyrimidine ring is achieved by two routes both involving a carbodiimide-mediated cyclization process, which allow incorporation of the amine functionality at C9 of the core tricyclic (six steps). Installation of the northeast 2-aminopyrimidine ring at C5 is performed using the Bredereck protocol (three steps). Ultimate, thermal decarboxylation with concomitant O-methyl deprotection and further N-benzyl deprotection by the action of triflic acid completed the synthesis of the target natural product variolin B. 相似文献
918.
The viability of nonaqueous capillary electrophoresis (NACE) was investigated for the simultaneous determination of tamoxifen, imipramine and their main metabolites (4-hydroxytamoxifen and desipramine, respectively). Baseline separation of the studied solutes was obtained on a 57 cm × 75 μm capillary using a nonaqueous solution composed of 17 mM ammonium acetate and 1.25% acetic acid in 80:20 (v:v) methanol-acetonitrile, temperature and voltage 22 °C and 15 kV, respectively, and hydrodynamic injection. Paroxetine was used as internal standard. Different aspects including linearity, accuracy, ruggedness and precision was studied. Detection limits between 9.0 and 15.0 μg L−1 were obtained for all the studied compounds. The developed method is simple, rapid and sensitive and has been used to determine tamoxifen, imipramine and their metabolites at clinically relevant levels in human urine. Before NACE determination, a solid phase extraction (SPE) procedure with a C18 cartridge was necessary. Real determination of these analytes in three females urines were done. 相似文献
919.
Glawe DD Rodríguez F Stone MO Naik RR 《Langmuir : the ACS journal of surfaces and colloids》2005,21(2):717-720
Herein, we describe the formation of silica structures on indium tin oxide (ITO) surfaces using poly-L-lysine (PLL) to template the condensation of silicic acid. Precisely controlled electrostatic fields were used to preposition PLL onto ITO surfaces. Subsequent polypeptide-mediated silicification resulted in the formation of silica with concentration gradients that followed the pattern of the externally applied electrostatic field used in the deposition of the PLL. The resulting silica structures were securely attached to the ITO surface. The technique described here offers an inexpensive and rapid method for the deposition of polypeptides on surfaces. 相似文献
920.
Antonio García Martínez Enrique Teso Vilar Santiago de la Moya Cerero 《Tetrahedron letters》2005,46(20):3509-3511
7,7-Dimethyl-2-methylenenorbornan-1-ol, a strained bicyclic 1-alkenyl cyclopentanol, undergoes Wagner-Meerwein rearrangement to fenchone under treatment with a catalytic amount of PdCl2(PPh3)2 in refluxing N-methylpyrrolidin-2-one. The described reaction constitutes the first example of the palladium(II)-catalyzed ring expansion of 1-alkenyl cyclopentanols to the corresponding cyclohexanones. 相似文献