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991.
The chiral phosphine‐oxazoline ligands 3 and 4 bearing 4‐alkoxymethyl substituents on the oxazoline ring with (R)‐configuration were prepared from L‐serine methyl ester in 66% and 33% yields, respectively. Along this synthetic pathway, the β‐hydroxylamides derived from L‐serine methyl ester and 2‐halobenzoyl chlorides were expediently converted to the corresponding oxazolines by using diethylaminosulfur trifluoride as the activation agent. Potassium diphenylphosphide was the reagent of choice for replacing the bromine atom on the phenyl ring, giving the desired oxazoline‐phosphine ligands 3 and 4 . Together with [Pd(η3‐allyl)Cl]2, ligands 3 and 4 induced an enantioselective allylic substitution reaction of 1,3‐diphenyl‐2‐pro‐penyl acetate by dimethyl malonate. Although ligands 3 and 4 exhibit the (R)‐configuration, differing from the (S)‐configuration of Pfaltz‐Helmchen‐Williams phosphine‐oxazoline ligands, all these ligands led to the same enantiotopic preference in the allylic substitution reaction. To facilitate the recovery and reuse of the phosphine‐oxazoline ligand, immobilization on Merrifield resin was attempted, albeit in low loading. 相似文献
992.
Platas-Iglesias C Esteban-Gómez D Enríquez-Pérez T Avecilla F de Blas A Rodríguez-Blas T 《Inorganic chemistry》2005,44(7):2224-2233
Compounds of formula [Pb(L2)(NCS)2] (1) and [Pb(L4)(SCN)2] (2) (where L2 is the lariat crown ether N,N'-bis(3-aminobenzyl)-4,13-diaza-18-crown-6 and L4 is the Schiff-base lariat crown ether N,N'-bis(3-(salicylaldimino)benzyl)-4,13-diaza-18-crown-6) were isolated and structurally characterized by X-ray diffraction analyses. The X-ray crystal structures of both compounds show the metal ion coordinated to the six donor atoms of the crown moiety, leaving the corresponding pendant arms uncoordinated. The coordination sphere of lead(II) is completed by two thiocyanate groups that coordinate either through their nitrogen (1) or sulfur (2) atoms. The organic receptor adopts a syn conformation in 1, while in 2 it shows an anti conformation. To rationalize these unexpected different conformations of the L2 and L4 receptors in compounds 1 and 2, as well as the different binding modes found for the thiocyanate ligands, we have carried out theoretical calculations at the DFT (B3LYP) level. These calculations predict the syn conformation being the most stable in both 1 and 2 complexes. So, the anti conformation found for 2 in the solid state is tentatively attributed to the presence of intermolecular pi-pi interactions between phenol rings, for which the dihedral angle between the least-squares planes of both rings amounts to 2.6 degrees and the distance between the center of both rings is 3.766 A. On the other hand, the analysis of the electronic structure has revealed that the Pb-ligand bonds present highly ionic character in this family of compounds. They also suggest a greater transfer of electron density from the NCS- ligands when they coordinate through the less electronegative S atom. The Pb-SCN covalent bond formation mainly occurs due to an effective overlap of the occupied 3p z orbitals of the S atoms and the unoccupied 6p z AO of the Pb atom, while the Pb-NCS bonding interaction is primarily due to the overlap of the 6s and 7s AO of Pb with sp(1.10) hybrids of the N donor atoms. Our electronic structure calculations can rationalize the different coordination of the thiocyanate groups in compounds 1 and 2: the simultaneous formation of two Pb-SCN bonds is more favorable for S-Pb-S angles close to 180 degrees , for which the overlap between the occupied 3p z orbitals of the S atoms and the unoccupied 6 pz AO of the Pb atom is maximized. 相似文献
993.
Alibés R Bayón P de March P Figueredo M Font J García-García E González-Gálvez D 《Organic letters》2005,7(22):5107-5109
[reaction: see text] A highly versatile approach to the enantioselective synthesis of securinega alkaloids is presented. Crucial steps are a palladium-catalyzed enantioselective imide alkylation, a vinylogous Mannich reaction, and a ring-closing metathesis process. Through this strategy, the synthesis of (-)-norsecurinine has been accomplished in nine steps and 11% overall yield. 相似文献
994.
Yong‐Min Lee Yoon‐Bo Shim Seung Jae Lee Sung Kwon Kang Sung‐Nak Choi 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(12):o733-o734
The structure of the title compound, C15H27N2+·ClO4?, consists of a monoprotonated sparteinium cation and a perchlorate anion. The two tertiary N atoms of the cation, one perchlorate O atom and a H atom form a bifurcated hydrogen bond, the four hydrogen‐bonding atoms being nearly in the same plane. 相似文献
995.
Gerhard Holxe Titus A. Jenny Petr Nesvadba Albert Gossauer Ludger Ernst Walter Keller Christoph Kratky 《Helvetica chimica acta》1991,74(6):1287-1295
On treatment with H2SO4/MeOH, epimerization of hexamethyl cis-5,6-dihydroxycobyrinate c,8-lactam ( 3 ) takes place quantitatively at C(6), yielding the corresponding trans-diol 4 . The corresponding lactone 7 , whose structure has been established by X-ray analysis, is obtained from xanthocorrinoids 5 and 6 under similar conditions. 相似文献
996.
Georges Dénès 《Journal of solid state chemistry》1981,37(1):16-23
The kinetics of the reconstructive first order phase transitions α → γ (upon heating) and β, γ → α (upon cooling) of SnF2 were studied by quantitative X-ray powder diffraction. The main feature of the kinetics is that these transformations are incomplete over a wide temperature range. Consequently it is not possible to fit the experimental data using the usual solid state rate expressions. Although these transitions are not reversible (large hysteresis) the empirical use of a kinetic model of a reversible transformation provides a good fit. The α → γ transformation was also investigated by D.T.A.; this transition was found to be greatly influenced by particle size: the transition temperature increases with grain size, and its enthalpy decreases. The X-ray investigation revealed that the process of the α → γ transformation involves an intermediate noncrystalline phase named the “transition phase.” It is suggested that the transition proceeds through a process of fragmentation-reconstruction. 相似文献
997.
Antonopoulos A Hardouin J Favetta P Helbert W Delmas AF Lafosse M 《Rapid communications in mass spectrometry : RCM》2005,19(16):2217-2226
Enzymatically digested oligosaccharides of kappa-, iota- and hybrid iota/nu-carrageenans were analysed using matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry in the negative-ion mode. nor-Harmane was used as matrix. Depending on the stock concentration and the laser intensity applied, the oligosaccharides exhibited losses of sulphate units (neutralised by the Na+ ion, and thus non-stable), leaving the primary backbone structure in most cases with only the deprotonated sulphate groups (carrying the negative charge, stable). This meant that kappa- and iota-oligosaccharides could not be easily distinguished from one another since they share the same primary backbone structure. However, for the hybrid iota/nu-oligosaccharides the primary backbone structure could be identified since the nu-carrageenan repeating unit differs from that of the kappa/iota-carrageenan unit. For all types of oligosaccharides, the results indicated cleavage of an anhydrogalactose unit from the non-reducing end. Specifically, for the hybrid oligosaccharides of iota/nu-carrageenans, this type of fragmentation means that the nu-carrageenan unit is not positioned on the non-reducing end of the hybrid oligosaccharides. Dehydration reactions, and exchange reactions of Na+ with K+ and Ca2+, were also observed. 相似文献
998.
Apostolidis A Lehmann H Schwotzer G Willsch R Prior A Wolfgang J Klimant I Wolfbeis OS 《Journal of chromatography. A》2002,955(2):183-189
On-line coupling continuous-flow liquid membrane extraction (CFLME) with HPLC, a novel automatic system was developed for the determination of sulfonylurea herbicides in water. After an automatic trace-enrichment process by CFLME, which is the combination of continuous flow liquid-liquid extraction and support liquid membrane (SLM) extraction, the target analytes were concentrated in 50 microl of 0.2 M Na2CO3-NaHCO3 (pH 10.0) buffer. The concentrated sample solutions were injected directly onto a C18 analytical column with a valve, and detected at 240 nm with a diode array detector. Metsulfuron methyl (MSM), and DPX-A 7881 were baseline separated with a mobile phase consisting of methanol and 67 mM KH2PO4-Na2HPO4 (pH 5.91) buffer (45+55, v+v) at a flow-rate of 1.0 ml min(-1). With an enrichment time of 10 min and enrichment sample volume of 20 ml, the enrichment factors and detection limits are 100 and 0.05 microg l(-1) for MSM, and 96 and 0.1 microg l(-1) for DPX-A 7881, respectively. The linear range and precision (RSD) are 0.1-50 microg l(-1) and 7.0% for MSM, and 0.2-50 microg l(-1) and 9.2% for DPX-A 7881, respectively. This proposed method was applied to determine MSM and DPX-A 7881 in seawater, tap water, and bottled mineral water with spiked recoveries in the range of 83-95% for MSM and 88-100% for DPX-A 7881, respectively. 相似文献
999.
The preparation and the properties of the hexacyanopalladium(IV) acid (H3O)2[Pd(CN)6] and of a number of metal hexacyanopalladates(IV) are described. UV, IR and Raman spectra are reported, force constants have been calculated and the bonding properties are discussed. K2[Pd(CN)6] crystallizes in a hexagonal lattice; a = 7.42, c = 6.65 Å, Z = 1. 相似文献
1000.
Iodide ions—in a rather narrow concentration range—induce some of the uncatalyzed bromate oscillators to a more pronounced oscillatory activity: the number of oscillations increases considerably and the overall rate of the chemical reaction drops about an order of magnitude. Preliminary suggestion is made on the mechanism of iodide-induced oscillatory reactions.
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