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981.
982.
Evgenyi V. Gryshkun Natalia V. Andrushko Oleg I. Kolodiazhnyi 《Phosphorus, sulfur, and silicon and the related elements》2013,188(6):1027-1046
Racemic chlorophosphines react stereoselectively with chiral l-phenylethylamines or amino acid esters to give diastereomerically enriched aminophosphines 3, which were isolated as diastereomerically pure crystalline borane complexes. Oxidation, thionation, the reaction with methyl iodide provide optically active derivatives of aminophosphines. (R,S)- and (S,S)-stereomers of phosphinic acid amides were separated by crystallization and a flash-chromatography. The stereochemical properties of phosphorus acid amides were investigated. The mechanism of asymmetric induction at the trivalent phosphorus atom was rationalized. 相似文献
983.
Anastasia O. Kolodiazhna Irina V. Guliaiko Oleg I. Kolodiazhnyi 《Phosphorus, sulfur, and silicon and the related elements》2013,188(10):2335-2346
Abstract The addition of silylphosphines to chiral aldehydes proceeds with high diastereoselectivity to give optically pure tertiary α -trimethylsiloxyalkylphosphines. The diastereomeric excesses of the addition products were achieved to 90–100%. The reaction of bis(trimethylsilyl)phenylphosphine with the acetonide of (R)-glyceraldehyde provides diastereomerically enriched tertiary bis(glyceryl)phosphines. 相似文献
984.
Sakae Uemura 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4):721-728
Retrospect of organoselenium and tellurium chemistry for these 30 years is described focusing on our novel findings in this field: (1) telluroxide elimination leading to alkenes and allylic compounds, (2) Pd-catalyzed or –mediated carbodetelluration for a new C–C bond formation, (3) synthesis of chiral diferrocenyl dichalcogenides and their use as chiral auxiliaries, (4) asymmetric selenoxide elimination for making optically active allenes and alkenes, (5) meta chloroperbenzoic acid (MCPBA) oxidation of organic selenides and tellurides leading to a substitution of a PhSe or PhTe moiety, as well as (6) preparation of chalcogen-bridged diruthenium complexes and their catalytic use for propargylic substitution reactions. 相似文献
985.
Liangru Yang Yunfei Li Pu Mao Jinwei Yuan Yongmei Xiao 《Phosphorus, sulfur, and silicon and the related elements》2013,188(8):780-788
AbstractThe catalytic activity of a series of chiral heteroaryl coordinated chelating N-heterocyclic carbene (NHC) palladium complexes towards asymmetric allylic alkylation (AAA) were presented here. The effects of different N-substituents, NHC backbones and chelate rings on the catalytic activity and the enantioselectivity of the alkylation of (E)-1,3-diarylallyl acetates with dialkyl malonate were investigated. The results showed that, under the optimized conditions, complexes 3a, 3b, and 3i carrying the pyridinyl-coordinated five-membered chelate ring showed high catalytic activity and chiral induction efficiency. The corresponding alkylated products were obtained in high yields with moderate ee. Furthermore, it was found that the substituents of (E)-1,3-diarylallyl acetates and the type of the nucleophile affect the results as well. 相似文献
986.
Bianca Flavia Bonini Luca Bernardi Mauro Comes-Franchini Gabriella Dessole Mariafrancesca Fochi Alfredo Ricci 《Phosphorus, sulfur, and silicon and the related elements》2013,188(5-6):1273-1277
Abstract Enantiomerically pure 2-hydroxyalkyl, 2-aminoalkyl and 2-iminoalkyl ferrocenyl p-tolylsulfides are easily prepared in good yields and with complete diastereocontrol from (S)-(2-p-tolylthio)ferrocencarboxyaldehyde. 2-Iminoalkyl ferrocenyl derivatives can be used as ligands in asymmetric catalysis and as starting materials for asymmetric Staudinger reaction. 相似文献
987.
Rob. J. M. Hermans Henk M. Buck 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4):255-265
Abstract An 1H NMR study of the conformation of the dioxaphosphorinane ring of a number of diastereoisomeric bicyclic saturated six-membered ring phosphites (3ab-10ab) has been performed. The dioxaphosphorinane ring of these phosphites is transannelated with a tetrahydrofuran, cyclopen-tane, tetrahydropyran or cyclohexane ring. The substituent on the phosphorus atom is a methoxy or phenoxy group. It is shown that the cis isomers 3a-10a prefer a chair conformation of the dioxaphosphorinane ring, independent of the substituent on the phosphorus atom and of the nature of the transannelated ring. In contrast, for the trans isomers 3b-10b a twist rather than a chair conformation of the dioxaphosphorinane ring is preferred. The fraction of the twist conformer in the trans isomers is mainly determined by the substituent on phosphorus. The size and composition of the transannelated ring are relatively unimportant in this respect. For both cis and trans isomers the preferred geometry is solvent-independent. The measured 3JPOCH couplings of the cis isomers 3a-10a are used to formulate an expression for the dependence of such couplings upon dihedral angles in bicyclic phosphites. 相似文献
988.
The analysis on the recovery performance and characteristics in shape memory effects is helpful for the optimal design and engineering applications of shape memory polymers and their composites. To investigate the relationships among recovery performance, material parameters, and loading conditions, by taking aliphatic polyether urethane as an example, the researchers simulate the shape memory behaviors numerically using a three‐dimensional viscoelastic model. The material parameters for this model are taken from stress relaxation tests, rather than dynamic mechanical analysis tests. Both the unconstrained and the constrained recovery behaviors during strain‐controlled shape memory processes are analyzed. The results reveal that the unconstrained recovery occurs at the same temperature regardless of the applied strain values. Another interesting result is that the shape recovery temperature in unconstrained recovery situations increases and the maximum recovery stress under constrained recovery conditions decreases with the increase of heating rates. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
989.
The present work attempts to study the mechanical properties and toughness behavior of a typical acrylic melamine clearcoat modified by a polyester‐amide hyperbranched polymer (HBP). Formulations were such that 0, 5, 10, 25 and 50% (molar percent) of total acrylic hydroxyl groups were stoichiometrically substituted by those of HBP. Bulk and surface of the clearcoats were studied by various mechanical techniques including hardness, tensile, dynamic mechanical thermal analysis (DMTA), nano‐indentation and scratch tests. In addition a scanning electron microscope (SEM) was utilized to observe the morphology of the fractured films. The bulk mechanical properties showed that a low loading (5 molar %) of HBP was sufficient to considerably increase the bulk hardness, cross‐linking density and toughness. DMTA and SEM results proved the occurrence of a single‐phase blend and that the shear deformation was the main toughening mechanism of HBP modified clearcoats. In general, it was revealed that the HBP not only could act as an excellent compatible toughening agent, but also maintained the clarity of the clearcoat and increased its scratch resistance. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
990.
Suizhou Yang Ke Yang Aloke Jain Ramaswamy Nagarajan Jayant Kumar 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(11):938-941
A novel method for maskless micro-patterning of polymeric substrates is presented. First, an azobenzene functionalized polymer film is spin-coated on a Poly (ethylene terephthalate) (PET) sheet. Then surface relief structures are optically inscribed on the polymer film by interference of laser beams. The patterned azobenzene functionalized film is then etched in the plasma chamber such that the gratings are transferred to the PET substrate. Finally, any remaining azobenzene functionalized polymer is dissolved away using an appropriate solvent. This method of patterning can be broadly applied to a variety of flexible/polymeric substrates and the resolution is not limited by the substrate thermo-mechanical properties. 相似文献