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91.
A highly enantioselective (up to 97.5% ee) and diastereoselective (95:5 dr trans/cis) Cu(I)-catalyzed cyclopropanation of alkenes using phenyliodonium ylide generated in situ from iodosobenzene and methyl nitroacetate is reported. The cyclopropanation took place with high enantioselectivity for a wide range of alkenes, and the reaction was performed at room temperature. 1-Nitrocyclopropyl esters are versatile building blocks to access the corresponding cyclopropane amino esters and aminocyclopropanes in two and three steps, respectively, from commercially available products. 相似文献
92.
The flocculation between the rod-like biopolymer Schizophyllan and two types of colloidal particles (latex with diameter 40 nm and alumina with diameter 60 nm) has been investigated by means of fluorescence correlation spectroscopy (FCS). The concentration ratio of Schizophyllan/particle q was varied in the range 0.1 approximately 20. Under conditions of pH about 5.7, 1 mmol.L(-1) NaCl, and room temperature (22+/-0.5 degrees C), the particles are strongly charged (alumina particles positively charged, latex negatively), while Schizophyllan is neutral. We observed that Schizophyllan chains flocculate with both types of particles, which suggests that the charge neutralization does not play a decisive role in these interactions. The ratio of fluorescence intensity of one floc over that of one particle, Q(f)/Q(p), and the corresponding hydrodynamic radius (r(h)) of the flocs have been measured. For a Schizophyllan-latex system, Q(f)/Q(p) reached a maximum value of 5 for q=3 indicating that the flocs contained five particles on average. The corresponding value of r(h) was r(h)=455 nm. The flocculation kinetic of latex particles with Schizophyllan was too fast to be measurable by FCS. For the Schizophyllan-alumina system, Q(f)/Q(p) was stable at about 1 in the whole studied range of q but r(h) increased with q suggesting that many Schizophyllan chains are adsorbed on individual particles. The flocculation kinetic of this system was studied by FCS and the obtained results were compatible with those of photon correlation spectroscopy. 相似文献
93.
A simple and general asymmetric synthesis of alpha-amino phosphonic acids is described. The method involves the highly selective addition of trialkyl phosphite onto various chiral oxazolidines. Oxazaphosphorinanes thus obtained with an excellent diastereoselectivity furnish the corresponding (S)-alpha-substituted amino phosphonic acids in good overall yields and high ee (77-->97%) after simple deprotection. 相似文献
94.
Hourdin M Gouhier G Gautier A Condamine E Piettre SR 《Journal of combinatorial chemistry》2005,7(2):285-297
Ten cross-linked polystyrene-supported, protected chiral amines featuring both a spacer, comprising from 5 to 15 atoms, and a fluorinated linker have been successfully prepared. The development of the monitoring technique by gel-phase 19F NMR spectrometry on cross-linked polystyrene derivatives proved to be of high value in four steps of the process, as shown by the comparison of data gathered from both a classic NMR spectrometer and elemental analysis. Gel-phase 19F NMR spectrometry, thus, constitutes a useful technique that complements IR and 13C NMR spectrometries for the qualitative monitoring of reactions. In addition, quantitative determination of the conversion in a given transformation is possible, provided that 19F chemical shifts of the substrate and the product be different enough (Deltadelta>base width), as illustrated by the Mitsunobu coupling process (16-->17). The technique is nondestructive, and the samples used to monitor the reactions may be returned to the reaction medium. Deprotection of the above amines was achieved and furnished eight of the final resins in good to acceptable purity for future applications. 相似文献
95.
Acidity measurements in trifluoroethanol and hexafluoroisopropanol as solvents, and in their mixtures with water, are reported. The hydrogen electrode and the glass electrode were used for pH measurements. The “experimental” autoprotolysis constants were determined from measurements in strongly acidic (trifluoromethanesulfonic) media and in strongly basic (alcoholate) media: for trifluoroethanol, pK = -log K/mol2 l-2 = 15 and for hexafluoroisopropanol, pK = 14.8. Evaluation of the pH-indicator potential systems with reference to the ferrocene/ferricinium couple gives the acidity function R0(H). The values obtained are compared to the H0 values evaluated in the same conditions. 相似文献
96.
Jacques Curély 《Monatshefte für Chemie / Chemical Monthly》2005,136(6):987-1011
Summary. The problem of direct exchange is examined in the simplest cases (formal coupling of two electrons initially isolated and hydrogen molecule). Then we consider the general case of a solid characterized by weak overlaps between the atomic orbitals of first-nearest neighbours so that the involved electrons are quasi-localized. We recall the physical origin of spin-orbit coupling. Its influence on direct exchange allows one to revisit Hunds rules and to express phenomenological Hamiltonians describing anisotropic couplings as well as the antisymmetrical Dzialoshinski-Moriya coupling. 相似文献
97.
Oxidation of some 2-(N,N-dimethylaminomethyl)ferrocenylalkylcarbinols by MnO2 is totally diastereoselective: only one diastereomer is oxidized. A study was performed to highlight the influential factors of this phenomenon. Several ferrocenyl alcohols have been studied. First, two diastereomers of the ferrocenyl amino alcohol bearing a deuterium as an R group have been synthesized and oxidized. The good reactivity of both diastereomers displayed the importance of the size of the alkyl group, which needs to be bulkier than a deuterium. The synthesis and the oxidation of endo- and exo-α-hydroxy [4](1,2)ferrocenophane enabled the elimination of the hypothesis involving the spatial position of the hydroxy group, while the two diastereomers were oxidized. The replacement of the dimethylamino group by a methoxy or a methyl, the oxidation of these compounds, and the study of the preferential conformation of each diastereomer showed clearly the influence of an intramolecular hydrogen bond. So,the diastereoselectivity was shown to depend on the steric bulk of the alkyl group and on the presence of a strong intramolecular hydrogen bond between the hydroxy group and the nitrogen. 相似文献
98.
Claude G. Andrieu Colette Chatain-Cathaud Marie Claude Fournié-Zaluski 《Journal of Molecular Structure》1974,22(3):433-444
The carbonyl bands of 2-formyl and 3-formyl-furans [18O] are determined and explained. The magnitude of the inductive and mesomeric effects in 2-acyl and 3-acyl-thiophenes and furans is discussed on the basis of a comparison of the frequencies and the intensities of the v(CO) and v(CC) bands. The conformational preference of some aroyl-furans and aroyl-formyl-furans and the rotation around the C(Ar)-C(O) bonds are related to these parameters. 相似文献
99.
The crystal structure of the fluorozirconate SmZrF7 has been determined from single crystal X-ray data; the final R value is 0.028. In this compound, isotypic with all the fluorozirconates LnZrF7 (Ln = rare earth), the symmetry of the cell is monoclinic (space group: P21). The Zr atoms are surrounded by six fluorine atoms forming an almost perfect octahedron: the average distance ZrF is 2.006 Å. The Sm atoms are surrounded by a 8 fluorine atoms polyhedron, the distances SmF lie from 2.221 to 2.411 Å. The association of these two polyhedra by sharing corner forms slabs with an approximately ReO3 type arrangement: the thickness of the slabs is two octahedra.These slabs with the composition M2X7 are held together so that the top fluorine atoms at the surface of a slab increase the coordination of the Sm atom of an adjacent slab. This MX3.5 phase corresponds to a new structural type between MX3 (ReO3 type) and MX4 (SnF4 type). 相似文献
100.
Peptide-based reversible and irreversible cysteine proteases inhibitors are well reported in the literature. Many of these compounds have an electrophilic carbonyl group as a cysteine trap in the place of a scissile amide moiety of the natural substrate. As a common mechanism strategy, we have designed a probe library of a cysteine trap for rapid optimization of P1-P1' pockets of different cysteine proteases. The synthesis of this library using a straightforward methodology based on polymer-supported reagents and scavengers to avoid tedious purification steps has been achieved. For the selective monobromination of diazo ketones, preparation of a new supported reagent, piperidinoaminomethylpolystyrene hydrobromide, is also described. 相似文献