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11.
The base-mediated rearrangement of epoxides into allylic alcohols is a well-known synthetic transformation. The first enantioselective version of the reaction using a chiral base was reported in 1980. Since then, the reaction has received a lot of attention mostly due to the great usefulness of chiral allylic alcohols in organic synthesis. Major breakthroughs in the area were the first report on using a sub-stoichiometric amount of chiral base, and the development of chiral bases for a true catalytic reaction protocol. The present review covers the time from when the first asymmetric epoxide isomerisation reaction was reported (1980) up to now, focusing on the period 1997-2001. 相似文献
12.
Burke RM Pearce JK Boxford WE Bruckmann A Dessent CE 《The journal of physical chemistry. A》2005,109(43):9775-9785
Multiply charged anions (MCAs) represent highly energetic species in the gas phase but can be stabilized through formation of molecular clusters with solvent molecules or counterions. We explore the intramolecular stabilization of excess negative charge in gas-phase MCAs by probing the intrinsic stability of the [adenosine 5'-triphosphate-2H](2-) ([ATP-2H](2-)), [adenosine 5'-diphosphate-2H](2-) ([ADP-2H](2-)), and H(3)P(3)O(10)(2-) dianions and their protonated monoanionic analogues. The relative activation barriers for decay of the dianions via electron detachment or ionic fragmentation are investigated using resonance excitation of ions isolated within a quadrupole trap. All of the dianions decayed via ionic fragmentation demonstrating that the repulsive Coulomb barriers (RCB) for ionic fragmentation lie below the RCBs for electron detachment. Both the electrospray ionization mass spectra (ESI-MS) and total fragmentation energies for [ATP-2H](2-), [ADP-2H](2-), and H(3)P(3)O(10)(2-) indicate that the multiply charged H(3)P(3)O(10)(2-) phosphate moiety is stabilized by the presence of the adenosine group and the stability of the dianions increases in the order H(3)P(3)O(10)(2-) < [ADP-2H](2-) < [ATP-2H](2-). Fully optimized, B3LYP/6-31+G* minimum energy structures illustrate that the excess charges in all of the phosphate anions are stabilized by intramolecular hydrogen bonding either within the phosphate chain or between the phosphate and the adenosine. We develop a model to illustrate that the relative magnitudes of the RCBs and hence the stability of these ions is dominated by the extent of intramolecular hydrogen bonding. 相似文献
13.
Angelika Baranowska Magdalena Siedlecka Andrzej J. Sadlej 《Theoretical chemistry accounts》2007,118(5-6):959-972
Recent studies of the perturbation-dependent basis sets have indicated the possibility of a significant reduction of the size
of the usual CGTO sets without considerable loss of accuracy in calculations of molecular electric properties. The resulting
(ZPolX) basis sets have been developed for several atoms of the first and second row of the Periodic Table. The same method
of the ZPolX basis set generation is extended for the first-row transition metals and the corresponding contracted ZPolX basis
sets of the size [6s5p3d1f] are determined for both nonrelativistic and scalar relativistic calculations. The performance
of the ZPolX basis sets is verified in calculations on the first-row transition metal oxides at the level of the ROHF, ROHF/CASPT2,
and ROHF/CCSD(T) approximations. Also the study of the dipole polarizability of TiCl4 confirms the excellent features of these very compact basis sets. The ZPolX basis sets for nonrelativistic and relativistic
calculations of molecular electric properties are available on the web page http://www.chem.uni.torun.pl/zchk/basis-sets.html. 相似文献
14.
The automation of all aspects of manual solution-phase synthesis into one integrated, efficient, and reliable system could be regarded as something of an unmet challenge in organic chemistry. The requirements for modern solution-phase libraries in mainstream drug discovery is typically 50-250 high-purity compounds on a 10-100-mg scale, whether for target class libraries or lead optimization, and short cycle time in combination with high capacity is critical. To achieve these goals, in a codevelopment between Aventis and Accelab GmbH, Kusterdingen, Germany, we designed a completely novel system of independent workstations connected by a shuttle transfer system produced by Montech, Derendingen, Switzerland. Seven modular workstations process four reactions on each shuttle in parallel, with the ability to perform synthesis (temperature control and liquid reagent handling), filtration, liquid-liquid extraction, evaporation, weighing, solid-phase extraction, and HPLC/MS analysis. The modular design enables the continuous loading of shuttles at any time, and each shuttle can have its own workflow. The design also allows easy expansion for future needs. The result is a combination of high flexibility and high throughput. 相似文献
15.
EPR, UV/Vis and FTIR spectroscopy as well as thermal analysis (TA/MS) were applied to study the influence of sulfate species present in the anatase support on the specific nature of VOx species in supported VOx/TiO2 catalysts. Those sulfate species modify the local structure of the supported vanadyl species and lead to the formation of two types of VO2+ sites instead of only one type being formed on sulfate‐free anatase. EPR and FTIR spectroscopic measurements revealed that a part of the VO2+ species are directly bound to the surface sulfate species. By TA/MS it was found that SO2 is released at lower temperature from VOx/TiO2 in comparison to the vanadium‐free support. The direct bonding between sulfate and VOx species stabilizes the latter on the surface of VOx/TiO2 resulting in three effects: 1) a higher V site dispersion in comparison to sulfate‐free TiO2, 2) a better resistance of surface vanadyls against diffusion into the bulk of the support and 3) a much faster reoxidation of reduced V sites than observed on sulfate‐free TiO2. 相似文献
16.
Angelika Basch Silvia Gross Namita Roy Choudhury Janis Matisons 《Journal of Sol-Gel Science and Technology》2005,33(1):39-45
New inorganic-organic hybrid materials were prepared by free-radical polymerization of methyl methacrylate (MMA) with methacrylate-substituted oxotantalum cluster [Ta4O4(OEt)8(OMc)4] and their properties evaluated. The cluster was prepared by the reaction of the parent alkoxide with methacrylic acid. Samples of the hybrid materials were produced with Ta-cluster to methyl methacrylate in the ratios of 1:50 and 1:100 and were characterized by thermal and spectroscopic techniques. The glass transition temperatures of the hybrid materials are shifted to higher temperatures than pure PMMA as a result of cross-linking of the polymer by the oxotantalum clusters. The increase in Tg is also observed from the dynamic mechanical analysis (DMA). Evidence of crosslinking between the Ta-cluster and PMMA is obtained from infrared spectroscopic study. Surface studies performed by X-ray photoelectron spectroscopy (XPS) provide information about the atomic concentrations of the surface and indicate tantalum bonded to oxygen. 相似文献
17.
Various condensed areno[g]lumazine derivatives 2 , 3 , and 5 – 7 were synthesized as new fluorescent aglycones for glycosylation reactions with 2-deoxy-3, 5-di-O-(p-toluoyl)-α/β-D -erythro-pentofuranosyl chloride ( 10 ) to form, in a Hilbert-Johnson-Birkofer reaction, the corresponding N1-(2′-deoxyribonucleosides) 15 – 21 . The β-D -anomers 15 , 17 , 19 , and 21 were deblocked to 24 – 27 and, together with N1-(2′-deoxy-β-D -ribofuranosyl)lumazine ( 22 ) and its 6, 7-diphenyl derivative 23 , dimethoxytritylated in 5′-position to 28–33. These intermediates were then converted into the 3′-(2-cyanoethyI diisopropylphosphoramidites) 34 – 39 which function as monomeric building block in oligonucleotide syntheses as well as into the 3′-(hydrogen succinates) 40 – 45 which can be used for coupling with the solid-support material. A series of lumazine-modified oligonucleotides were synthesized and the influence of the new nucleobases on the stability of duplex formation studied by measuring the Tm values in comparison to model sequences. A substantial increase in the Tm is observed on introduction of areno[g]lumazine moieties in the oligonucleotide chain stabilizing obviously the helical structures by improved stacking effects. Stabilization is strongly dependent on the site of the modified nucleobase in the chain. 相似文献
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20.
Amin Moosaie Anne Le Duc Michael Manhart 《ournal of non Newtonian Fluid Mechanics》2010,165(9-10):551-554
A normalization scheme for the numerical solution of the moment approximation equation in fiber suspension flows is presented. Here, normalization refers to rescaling the trace of the second moment tensor to unity at each time step. The equivalence between the normalization scheme and the quadratic closure model is analytically proved. The performance of the scheme is investigated in simple shear flow with respect to the quadratic and hybrid closures, and a stochastic Monte-Carlo simulator that provides exact solution. The proposed scheme is a computationally efficient alternative to the quadratic closure: it performs equally well and is more efficient regarding computational time. 相似文献