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991.
A series of C4-keto-functionalized 1-[(benzoyloxy)(ethoxycarbonyl)methyl]-2-azetidinones were prepared and studied for their tendency to undergo a Reformatsky-type cyclization to fused bicyclic or tricyclic beta-lactams with the single-electron reducing agent samarium diiodide. Whereas the azetidinone 21a underwent reductive cyclization, affording the potent antibiotic sanfetrinem's tricyclic [4.5.6] core structure as the major component, all other examples tested resulted in cyclization followed by an N to O acyl migration involving cleavage of the beta-lactam ring as the favored pathway. Highly functionalized proline derivatives were therefore accessed as single diastereomers through the reductive cyclization of benzoates 21b, 22, 23a,b, 24b, and 25-28. Pertinent for the success of these cyclizations was the addition of 1 equiv of tert-butyl alcohol, allowing for the protonation of the basic amide derivative obtained after the acyl migration step. The diastereoselectivities of these reactions deviate from those of similar cyclizations involving the corresponding lithium enolate. This divergence could be rationalized by the coordination of the metal ion of the samarium(III) enolate intermediate to the beta-lactam amide functionality in the cyclization step, which may not be possible for lithium enolates. 相似文献
992.
Kuo NN Huang JJ Miksovska J Chen RP Larsen RW Chan SI 《Journal of the American Chemical Society》2005,127(48):16945-16954
As part of our continuing study of the effects of the turn sequence on the conformational stability as well as the mechanism of folding of a beta-sheet structure, we have undertaken a parallel investigation of the solution structure, conformational stability, and kinetics of refolding of the beta-sheet VFIVDGOTYTEV(D)PGOKILQ. The latter peptide is an analogue of the original Gellman beta-sheet VFITS(D)PGKTYTEV(D)PGOKILQ, wherein the TS(D)PGK turn sequence in the first hairpin has been replaced by VDGO. Thermodynamics studies revealed comparable conformational stability of the two peptides. However, unlike the Gellman peptide, which showed extremely rapid refolding of the first hairpin, early kinetic events associated with the refolding of the corresponding hairpin in the VDGO mutant were found to be significantly slower. A detailed study of the conformation of the modified peptide suggested that hydrophobic interactions might be contributing to its stability. Accordingly, we surmise that the early kinetic events are sensitive to whether the formation of the hairpin is nucleated at the turn or by sequestering of the hydrophobic residues across the strand, before structural rearrangements to produce the nativelike topology. Nucleation of the hairpin at the turn is expected to be intrinsically rapid for a strong turn. However, if the process must involve collapse of hydrophobic side chains, the nucleation should be slower as solvent molecules must be displaced to sequester the hydrophobic residues. These findings reflect the contribution of different forces toward nucleation of hairpins in the mechanism of folding of beta-sheets. 相似文献
993.
One-dimensional (1-D), two-dimensional (2-D), and three-dimensional (3-D) coordination polymers were prepared by self-assembly of binary metal complex systems, copper(II) nitrate and (en)Pt(II)(nic)(2) or (dmpda)Pt(II)(isonic)(2) (en = ethylenediamine, dmpda = 2,2'-dimethyl-1,3-propanediamine, nic = nicotinate, and isonic = isonicotinate), in aqueous solutions. Equimolar reactions of copper(II) nitrate with (dmpda)Pt(II)(isonic)(2) and (en)Pt(II)(nic)(2) resulted in 1-D ([(dmpda)Pt(isonic)(2)Cu(OH(2))(3)](NO(3))(2))(n)() (1) and 2-D ([(en)Pt(nic)(2)Cu(OH(2))](NO(3))(2))(n) (2), respectively, but the reaction of (en)Pt(II)(nic)(2) with excess copper(II) nitrate gave 3-D ([((en)Pt(nic)(2))(3)Cu(5)(OH)(2)(OH(2))(6)](NO(3))(8))(n) (3). The local structure of crystal 1 has a mononuclear copper unit, 2 has a dinuclear copper unit with a Cu-Cu distance of 2.659(5) A, and 3 has a pentanuclear copper unit. The methyl groups of the dmpda ligand are located in the space between two isonicotinate ligands of 1, which is presumed to be an important factor to determine the final structure of the crystal formed by self-assembly. Magnetic behaviors of crystals 1-3 examined in the temperature range of 4-300 K appear to be governed by the local structures around the copper(II) ions and do not indicate any significant long-range magnetic exchange interactions along the polymeric chain. 相似文献
994.
McDonnell C López O Murphy P Fernández Bolaños JG Hazell R Bols M 《Journal of the American Chemical Society》2004,126(39):12374-12385
The effect of conformation on glycoside reactivity was investigated by studying the hydrolysis of a selection of 3,6-anhydroglucosides as models for glucose in the highly reactive (1)C(4) conformation. Methyl 3,6-anhydro-beta-D-glucopyranoside was found to hydrolyze 200-400 times faster than methyl glucosides in the (4)C(1) conformation, while methyl 3,6-anhydro-beta-D-galactopyranoside, which is in the B(1,4) conformation, was less reactive than methyl beta-D-galactopyranoside. Methyl (3,6-anhydro-beta-D-glucopyranosyl)-(1 --> 6)-alpha-D-glucopyranoside, methyl (3,6-anhydro-alpha-D-glucopyranosyl)-(1 --> 6)-alpha-D-glucopyranosyl-(1 --> 6)-alpha-D-glucopyranoside, and methyl (3,6-anhydro-beta-D-glucopyranosyl)-(1 --> 6)-alpha-D-glucopyranosyl-(1 --> 6)-alpha-D-glucopyranoside were prepared and found to react selectively at the anhydro residue. The finding that (1)C(4) conformers of glucosides are highly reactive species is in accordance with and supports previous results showing that axial OH groups are less electron withdrawing than equatorial OH groups. 相似文献
995.
An acid vapor partial digestion procedure for bovine liver is proposed using a focused microwave oven and a laboratory-made PTFE support. The support is equipped with three cups of approximately 4 ml volume each one and the cups were adapted to the glass reaction vessel of the microwave oven. A mixture containing HNO3 plus H2SO4 is heated to 120 °C to generate acid vapor. Bovine liver (50-90 mg) were directly weighed into the cups followed by addition of a mixture containing NaClO+H2O2. Samples were exposed to acid vapor during 15-25 min and then diluted with distilled and deionized water to final masses of 3.0 g. Recoveries of Al, Ca, Cu, Fe, Mg, Mn, and Zn were evaluated using an ICP-OES with axially-viewed configuration. The effects of both particle sizes and acid vapor exposure time were evaluated and recoveries of most elements were quantitative when using 25 min of heating and 50 mg of samples. Slightly better recoveries were reached using particles smaller than 44 μm, but this effect was mainly observed for hardly extracted elements such as Al and Fe. 相似文献
996.
Rita?Patakfalvi Zsanett?Virányi Imre?DékányEmail author 《Colloid and polymer science》2004,283(3):299-305
Silver nanoparticles were prepared in aqueous AgNO3 solution by using hydroquinone and sodium citrate as reducing agents with neutral polymers poly(vinylpyrrolidone) and poly(vinyl alcohol) as stabilizers. The rate of particle formation was determined with a diode array UV-Vis spectrophotometer. The effects of the polymer concentration on the reaction rate, the size, and the size distribution of the particles formed were studied by transmission electron microscopy. Both the reaction rate and the size of silver nanoparticles decreased with increasing polymer concentration in the range 0.07–0.50 w/v%. 相似文献
997.
Essential oil composition of the leaves and stems of Meum athamanticum Jacq., from Spain 总被引:3,自引:0,他引:3
Palá-Paúl J García-Jiménez R Pérez-Alonso MJ Velasco-Negueruela A Sanz J 《Journal of chromatography. A》2004,1036(2):245-247
The essential oil of the leaves and stems of Meum athamanticum Jacq., has been extracted by steam distillation and analysed by gas chromatography (GC) and gas chromatography coupled to mass spectrometry (GC-MS). The monoterpene fraction was predominant while the sesquiterpene one was practically absent. The principal constituents have been identified as (E)-beta-ocimene (29.6%), gamma-terpinene (17.9%), terpinolene (17.0%) and p-cymene (9.7%). Our results show that the chemical composition of the essential oil obtained of the leaves and stems of M. athamanticum from Spain is different to that obtained from plants of Germany, Italy and France. 相似文献
998.
Imines of glycine alkyl esters react with imines in a diastereo- and highly enantioselective Mannich reaction in the presence of chiral copper(I) complexes as the catalyst to give optically active alpha,beta-diamino acid derivatives. A series of imines of glycine esters derived from glycine and aromatic carbonyl compounds has been screened as substrates for the Mannich reaction with different imines in the presence of various combinations of metal salts and chiral ligands. The benzophenone imine of glycine esters was found to react with N-protected imines in a diastereoselective fashion giving functionalized alpha,beta-diamino acid esters with excellent enantioselectivities. The most effective chiral catalysts are chiral copper(I) complexes having phosphino-oxazoline (P,N)-ligands, and among these ligands, those derived from (1R,2S)-dihydroxy-1,2,3,4-tetrahydronaphthalene gave the best results. The scope of this new catalytic asymmetric reaction of the benzophenone imine glycine esters is demonstrated for the reaction with different N-protected-C-aryl and C-alkyl imines giving the Mannich adducts with excellent optical purity. Furthermore, the synthetic aspects of the reaction are presented by converting the Mannich adducts into alpha,beta-diamino acid derivatives. The relative and absolute configuration of the Mannich adduct have been determined and based on the stereochemical outcome of the reaction a tetrahedral chiral-copper(I)-imino glycine alkyl ester intermediate is proposed. In this intermediate the Re-face of the benzophenone imine glycine ester is shielded by the chiral ligand leaving the Si-face available for approach of the Si-face of the imine. A series of semiempirical calculations has been performed to support the structure of the tetrahedral chiral-copper(I) complex and to account for the influence of the substituents in the chiral phosphino-oxazoline ligands. 相似文献
999.
Stanna-Brook rearrangement of carboxylic acid derivatives. Synthetic utility and mechanistic studies
[reaction: see text] The reaction of R(3)SnLi with carboxylic acid derivatives proceeds through a novel, very fast stanna-Brook rearrangement that generates alpha-alkoxyorganolithium compounds as intermediates. The outcome of these reactions depends on the nature of the carboxyl derivatives. Reaction of R(3)SnLi with ester derivatives gives rise to coupled products through a novel C-C bond formation reaction. Experimental evidence of the detailed reaction mechanism is provided. 相似文献
1000.
Vicente J Chicote MT Guerrero R Vicente-Hernández I Jones PG 《Inorganic chemistry》2003,42(23):7644-7651
The reaction of AgClO(4) and NH(3) in acetone gave [Ag(NH=CMe(2))(2)]ClO(4) (1). The reactions of 1 with [RhCl(diolefin)](2) or [RhCl(CO)(2)](2) (2:1) gave the bis(acetimine) complexes [Rh(diolefin)(NH=CMe(2))(2)]ClO(4) [diolefin = 1,5 cyclooctadiene = cod (2), norbornadiene = nbd (3)] or [Rh(CO)(2)(NH=CMe(2))(2)]ClO(4) (4), respectively. Mono(acetimine) complexes [Rh(diolefin)(NH=CMe(2))(PPh(3))]ClO(4) [diolefin = cod (5), nbd (6)] or [RhCl(diolefin)(NH=CMe(2))] [diolefin = cod (7), nbd (8)] were obtained by reacting 2 or 3 with PPh(3) (1:1) or with Me(4)NCl (1:1.1), respectively. The reaction of 4 with PR(3) (R = Ph, To, molar ratio 1:2) led to [Rh(CO)(NH=CMe(2))(PR(3))(2)]ClO(4) [R = Ph (9), C(6)H(4)Me-4 = To (10)] while cis-[Rh(CO)(NH=CMe(2))(2)(PPh(3))]ClO(4) (11) was isolated from the reaction of 1 with [RhCl(CO)(PPh(3))](2) (1:1). The crystal structures of 5 and [Ag[H(2)NC(Me)(2)CH(2)C(O)Me](PTo(3))]ClO(4) (A), a product obtained in a reaction between NH(3), AgClO(4), and PTo(3), have been determined. 相似文献