Enantioselective Conjugate Addition of Diethylzinc to Chalcone Catalyzed by Ni（acac）2 and Chiralβ-Amino Alcohols

Enantioselectivge conjugate addition of diethyzinc to chalcone was carried out in the presenee of Ni (acac)2 complexed with five pyrrolidfumyimethanois derived from L-proline. (S)-N-Benzyl-2-(l-hydroxy.l-methylethyl) pyrrolidlne was found to be the best ngnd in asymmetric conjugate addition among the five ligands. The products were obtained with up to 70% ee.The configuration of the product was determined jointly by the substituents on the carbon of the hydroxy group and the nitrogen atom.     

The Properties of an HBV Surface Antigen Protein Carrying the Binding Site for the Receptor of Hepatocytes——Its Formation of Surface Antigen Particles and Secretion From Discrete Cell Lines

A human hepatitis B virus (HBV) gene, which encodes the major surface antigen protein(S protein) carrying the hepatocyte receptor-binding site, was constructed with site-directed mutagenesis and in vitro recombination. When expressed in monkey kidney cell line COS-M6, this gene product (S309 protein) formed surface antigen (HBsAg) particles and secreted from the cells. It was stable within the cells and in the culture medium and could be immunoprecipitated with antisera directed against plasma-derived HBsAg or synthetic preS1 polypeptide. Isopycnic CsCl gradient centrifugation showed that the density of S309 protein particles (1.25 g/ml) was slightly higher than that of S protein particles. The S309 protein was readily secretable from hepatoma cell lines, and the amount secreted was comparable to that of the S protein. By contrast, only about 10% of the S309 protein was secreted from COS-M6 cells, and its appearance in culture medium was delayed. The efficiency of the secretion of the S309 protein can b     

Regioselective addtion of 5-amino-3-benzylthio-l,2,4-triazole and its analogues with aryl isocyanates

The orientation of the addition of 5-amino-3-benzylthio-1,2,4-triazole and its analogues (pyrazole) (1) with the aryl isocyanate can be directed by controlling the reaction temperature and one of the product, 5-amino-1-arylaminocarbonyl-3-benzylthio-1,2,4-triazole (pyrazole) (2), can rearrange at 170C to another product, 5-arylureylene-3-benzylthio-1,2,4-triazole (pyrazole) (3). A plausible mechanism explanation for this rearrangement reaction was presented. It was suggested that the rearrangement reaction could be referred to the thermodynamics transposition leading to the predominant 5-arylureylene-3-benzylthio-1,2,4-triazole energy preferentially.     

An efficient and facile procedure for synthesis of octyl polyglucoside

Nonionic surfactant alkyl polyglucoside (APG) was prepared by direct glycosidation of alkyl alcohol with glucose in the presence of sulfate acid-silica gel (H_2SO_4/SiO_2) as solid acidic catalyst.The quantity of catalyst was only of 1 wt%,based on the glucose,and the conversion of glucose was close to 100% at 110℃in 1.5h.The product was characterized by FT-IR,mass and ~1H NMR spectra.The degree of polymerization (DP) of the glucose in the product was 1.37,and critical micelle concentration (CMC) of product was only 0.0104 wt%.     

Theoretical Studies on the Mechanism of Photocycloaddition Reaction Between 6 Azauracil and Acetone

The mechanism of photocycloaddition reaction between 6-azauracll and acetone was studied by using semiemptrical SCFMO AMI method. It was found that this reaction is not a concerted one. The calculated results are as follows:(1) A T1 state exciplex is on the T1 state energy surface; (2) T exciplex as a reactant will proceed along the energy surface of T1 state to form a diradical intermediate. The energy barrier of this reaction step is 63. 6 kJ/mol; (3) The T1 state diradical intermediate happens to be close in energy to the ground state intermediate with a similar geometry. Such a situation turns out to be very favorable for an intersystem crossing (jump from the T, state to the ground state) ; (4) The final product will be formed from the ground S0 state intermediate via an energy barrier 88. 2 kJ/mol.     

Taguchi Optimization for Combustion Synthesis of Aluminum Oxide Nano-particles

Nano-structured aluminum oxide powders were prepared by a combustion synthesis method utilizing serine as a new fuel. The product was sonicated to obtain nano powders. A Taguchi L-4 statistical design of combustion synthesis was utilized to optimize the production of γ-alumina powder. The product was characterized by XRD, BET, SEM, EDX and LLS. Nano crystalline γ-alumina with crystal sizes between 4.26 and 5.47 nm and α-Al2O3 powders with crystal sizes 24.51 and 28.62 nm were obtained by the combustion synthesis. The specific surface area was measured by a BET method to be 75.21 m2/g. The average particle size after sonication of product, observed by LLS, was 79.32 nm.     

Radical Addition and Substitution Reactions of (η6-Arene)-tricarbonylmetal Complexes

We report here the first alkyl radical additions of (η6-arene)tricarbonylmanganese complexes in the presence of alkylmercury chloride and NaI (Eq. 1). The mechanism was postulated to be the alkyl radical addition to ArMn- (CO)+3 cation to form the corresponding 17 valence electron intermediate, which was then reduced by alkylmercury chloride via a single electron transfer process to afford the product and regenerate an alkyl radical. [1]     

Polarographic immunoassay coupled with catalytic amplification of labeled copper ions

A new approach of polarographlc immunoassay based on the catalytic amplification of the labeled metal ions and the polarographlc detection of the catalytic product was developed.In this approach,the copper ions used as the catalyst for substrate conversion instead of natural enzyme were labeled to model antigen diphtheria toxoid (DT) through the bifunctional chelating reagent diethylenetriamine pentaacetic acid (DTPA).After heterogeneous competitive imrnunoreaction,the oxidation of substrate o-phenylenediatnine (OPD) was catalyzed by the labeled copper ions to generate an electroactive product 2,3-diammophenazine (DAP); subsequently,the product DAP was detected with linear-sweep polarography The proposed assay can determine the concentration in the range of 10-1 000 ng/mL of DT,two orders of magnitude more sensitive than those based on the direct detection of the metal ion labels The proposed immunoassay can be applied to detecting various proteins of interest.     

Thermal decomposition of Pr[(C_5H_8NS_2)_3(C_(12)H_8N_2)]

The thermal behavior of the complex Pr[(C5H8NS2)3(C12H8N2)] in a dry nitrogen flow was examined by TG-DTG analysis. The TG-DTG investigations indicated that Pr[(C5H8NS2)3-(C12H8N2)] was decomposed into Pr2S3 and deposited carbon in one step where Pr2S3 predominated in the final products. The results of non-isothermal kinetic calculations showed that the decomposition stage was the random nucleation and subsequent growth mechanism (n = 2/3), the corresponding apparent activation energy ?was 115.89 kJ·mol-1 and the pre-expo-nential constant ln[A/s] was 7.8697. The empirical kinetics model equation was proposed as/(α) =3/2(1-α)[-ln(1-α)]1/3.The X-ray powder diffraction patterns of the thermal decomposition products at 800℃under N2 atmosphere show that the product can be indexed to the cubic Pr2S3 phase. The transmission electron microscopy (TEM) of the final product reveals the particle appearance of a diameter within 40 nm. The experimental results show that the praseodymium sulfide nanocrystal can be prepared from thermal decomposition of Pr[(C5H8NS2)3(C12H8N2)].     

Stereocontrol of the Schiff Base of Substituted Benzaldehyde to Staudinger Cycloaddition Reaction

Syntheses of 4 novel chiral azetidin-2-one derivatives,which were characterized by ^1H NMR,IR,specific rotation and elemental analysis,through Staudinger cycloaddition reaction of Schiff base of benzaldehyde with chlorine substitution at different position in benzene ring,were described.For the first time,this type of 3S,4R configuration azetidin-2-one monocrystals with many chiral centers [(3S,4R)-3-hydroxy-N-[(S)-(1-phenyl)ethyl]-4-(2‘‘-chlorophenyl)-azetidin-2-one monocrystal]were obtained,the structures of which were determined by X-ray diffraction analysis.The effects of Schiff base of benzaldehyde with chlorine substitution at different position in benzene ring on stereoselectivity of Staudinger cycloaddition reaction products were discussed and the results are showed as below:2-chlorophenyl Schiff base favored to yield 3S,4R configuration product,but 4-chlorophenyl Schiff base favored to yield 3R,4S configuration product.The reaction orientation of 2,4-dichlorophenyl Schiff base was determined by corporate effect of 2- and 4-chlorine,and that of the 4-chlorine was more obvious.In contrast to 4-chlorophenyl,although the main product was 3R,4S configuration,3-chlorophenyl owned lower selectivity.     

Synthesis of (+)-zeylenone from shikimic acid

Starting from shikimic acid, the total synthesis of zeylenone was studied. The product was proved to be the (+)antipode of zeylenone through analysis and comparison of their respective spectra (including NMR, MS, IR and CD) and optical data. The absolute configuration of the natural product was thus determined to be (1S,2S,3R).     

Stabilization of zeylenone in rat plasma by the presence of esterase inhibitors and its LC‐MS/MS assay for pharmacokinetic study

Six esterase inhibitors, namely EDTA·2Na⁺, NaF, phenylmethanesulfonyl fluoride, dichlorvos, bis‐nitrophenyl phosphate (BNPP) and thenoyltrifluoroacetone, and the mixture of NaF and BNPP, were evaluated for the stabilization of labile benzoate containing zeylenone in rat plasma. The mixture appeared to exhibit the most effectively stabilizing effect with the degraded content of zeylenone decreasing from >60% (in the absence of inhibitors) to <6%. Following the stabilization by the addition of NaF (5 mm ) and BNPP (5 mm ), the analytes in rat plasma were acidified by formic acid and extracted into ethyl acetate at 0°C. After chromatographic separation, the detection of zeylenone was performed on a 3200 Q‐Trap with positive ion electrospray mode, monitoring the ion transition m/z 383.2 → 105.0. The method was validated over the range from 2.68 to 1340 ng/mL with inter‐ and intra‐run precision for the quality control samples being less than 6.8%. The assay accuracy was within 100 ± 7.0%. The validated method was successfully applied to a pharmacokinetic study in rats after the intratracheal administration of zeylenone in free drug or polymeric micellar solutions. The results showed that the pulmonary absorption of zeylenone loaded in micelles was significantly retarded compared with that of free drug solutions. Copyright © 2012 John Wiley & Sons, Ltd.     

(S)-美托洛尔的不对称合成

用自制的(S,S)-Salen Co(Ⅲ)OAc催化剂水解动力学拆分外消旋环氧氯丙烷得到高光学纯的(S)-3-氯-1,2-丙二醇和较高光学纯的(R)-环氧氯丙烷。 以(S)-3氯-1,2-丙二醇为手性原料和4-(2-甲氧基乙基)苯酚缩合,再与氯化亚砜反应得环状亚硫酸酯,最后和异丙胺反应得(S)-美托洛尔,光学纯度大于99%。 另外以(R)-环氧氯丙烷为手性原料和4-(2-甲氧基乙基)苯酚反应,再与异丙胺作用得到(S)-美托洛尔,光学纯度大于92%。 (S)-美托洛尔的总收率为53.9%,结构经IR、1H NMR、13C NMR和MS测试技术确证。 该路线原料利用率高,拆分后的2种产物均能用于目标化合物的合成。     

Determination of the stereochemistry of 2-succinyl-5-enolpyruvyl-6-hydroxy-3- cyclohexene-1-carboxylate, a key intermediate in menaquinone biosynthesis

The turnover product of the committed step of menaquinone biosynthesis was isolated and determined to be (1R,2S,5S,6S)-2-succinyl-5-enolpyruvyl-6-hydroxy-3-cyclohexene-1-carboxylate. Structural determination of this key intermediate represents a critical step to complete elucidation of the biosynthetic pathway.     

Asymmetric synthesis of novel thioiso dideoxynucleosides with exocyclic methylene as potential antiviral agents

Novel thioiso pyrimidine and purine nucleosides substituted with exocyclic methylene have been synthesized, starting from D-xylose. The glycosyl donor 14 was synthesized from D-xylose, using cyclization of dimesylate 10 with sodium sulfide as a key step. Cyclization proceeded in pure S(N)2 reaction without going through S(N)1 reaction in the presence of an allylic functional group at low reaction temperature (0 degrees C) in polar solvent (DMF), affording compound 12 as a major product. At higher temperatures, S(N)2' product 11 was almost exclusively obtained as a major product. On the other hand, glycosylation of 14 with 6-chloropurine under Mitsunobu conditions afforded the desired S(N)2 product 26, while palladium-catalyzed glycosylation resulted in the sole formation of S(N)2' product 34.     

Synthetic study of optically active 3-azabicyclo[3.3.0]octane-2,6,8-tricarboxylic acid

Synthesis of (1R,2S,5S,6R,8S)-3-azabicyclo[3.3.0]octane-2,6,8-tricarboxylic acid (2) from trans-4-hydroxy-L-proline (5) was attempted. A Diels-Alder reaction of 3,4-dehydroproline derivative 9 and cyclopentadiene afforded a single stereoisomer 11. The Diels-Alder adduct was smoothly converted to the hydrochloride of 2 (24) via RuO(4) oxidation. Although some racemization of the material or product was observed during the synthetic processes, the amino acid 24 proved to be optically pure.     

Additive effects of amines on asymmetric hydrogenation of quinoxalines catalyzed by chiral iridium complexes

The additive effects of amines were realized in the asymmetric hydrogenation of 2-phenylquinoxaline, and its derivatives, catalyzed by chiral cationic dinuclear triply halide-bridged iridium complexes [{Ir(H)[diphosphine]}(2) (μ-X)(3) ]X (diphosphine=(S)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl [(S)-BINAP], (S)-5,5'-bis(diphenylphosphino)-4,4'-bi-1,3-benzodioxole [(S)-SEGPHOS], (S)-5,5'-bis(diphenylphosphino)-2,2,2',2'-tetrafluoro-4,4'-bi-1,3-benzodioxole [(S)-DIFLUORPHOS]; X=Cl, Br, I) to produce the corresponding 2-aryl-1,2,3,4-tetrahydroquinoxalines. The additive effects of amines were investigated by solution dynamics studies of iridium complexes in the presence of N-methyl-p-anisidine (MPA), which was determined to be the best amine additive for achievement of a high enantioselectivity of (S)-2-phenyl-1,2,3,4-tetrahydroquinoxaline, and by labeling experiments, which revealed a plausible mechanism comprised of two cycles. One catalytic cycle was less active and less enantioselective; it involved the substrate-coordinated mononuclear complex [IrHCl(2) (2-phenylquinoxaline){(S)-BINAP}], which afforded half-reduced product 3-phenyl-1,2-dihydroquinoxaline. A poorly enantioselective disproportionation of this half-reduced product afforded (S)-2-phenyl-1,2,3,4-tetrahydroquinoxaline. The other cycle involved a more active hydride-amide catalyst, derived from amine-coordinated mononuclear complex [IrCl(2) H(MPA){(S)-BINAP}], which functioned to reduce 2-phenylquinoxaline to (S)-2-phenyl-1,2,3,4-tetrahydroquinoxaline with high enantioselectivity. Based on the proposed mechanism, an Ir(I) -JOSIPHOS (JOSIPHOS=(R)-1-[(S(p) )-2-(dicyclohexylphosphino)ferrocenylethyl]diphenylphosphine) catalyst in the presence of amine additive resulted in the highest enantioselectivity for the asymmetric hydrogenation of 2-phenylquinoxaline. Interestingly, the reaction rate and enantioselectivity were gradually increased during the reaction by a positive-feedback effect from the product amines.     

Carbapenem biosynthesis: confirmation of stereochemical assignments and the role of CarC in the ring stereoinversion process from L-proline

(5R)-Carbapen-2-em-3-carboxylic acid is the simplest structurally among the naturally occurring carbapenem beta-lactam antibiotics. It co-occurs with two saturated (3S,5S)- and (3S,5R)-carbapenam carboxylic acids. Confusion persists in the literature about the signs of rotation and absolute configurations of these compounds that is resolved in this paper. (3S,5S)-Carbapenam carboxylic acid was prepared from L-pyroglutamic acid to unambiguously establish its absolute configuration as identical to the natural product isolated from Serratia marcescens and from overexpression of the biosynthetic genes carAB in Escherichia coli. L-Proline labeled with deuterium or tritium at the diastereotopic C-5 methylene loci was shown to incorporate one label at the bridgehead of (3S,5S)-carbapenam carboxylic acid, but not into the "inverted" (3S,5R)-carbapenam carboxylic acid or the final carbapenem product. CarC, the third enzyme of the biosynthetic pathway required to synthesize the carbapenem, was demonstrated in cell-free studies to be dependent on alpha-ketoglutarate and ascorbate in keeping with weak sequence identities with other non-heme iron, alpha-ketoglutarate-dependent oxygenases. CarC mediated the stereoinversion of synthetic (3S,5S)-carbapenam carboxylic acid to the (5R)-carbapenem as judged by bioassay. These findings suggest that L-proline is desaturated to pyrroline-5-carboxylic acid prior to uptake into the biosynthetic pathway. The loss of the bridgehead hydrogen from the (3S,5S)-carbapenam during the ring inversion process to form the epimeric (3S,5R)-carbapenam and desaturation to the (5R)-carbapenem are proposed to be coupled by CarC to the reduction of dioxygen to drive the formation of these higher energy products, an unprecedented reaction for this enzyme class.     

生物油水蒸气气化实验研究

利用固定床反应器对生物油的水蒸气非催化气化性能进行了实验研究,考察了温度和水蒸气的加入量对气化过程的影响,对气化所得粗合成气的组成分布进行了分析。结果表明,升高温度有利于生物油向合成气转化,1 200 ℃时,生物油的碳转化率可达97.8%,合成气有效成分(H₂+CO)的产率可达77%,其中H₂/CO摩尔比为1.19;水蒸气的加入可以提高合成气中的H₂/CO摩尔比,当S/C(水碳比)=4时,合成气中的H₂/CO摩尔比可达3.69,与此同时,水蒸气的加入不利于合成气有效成分产率的提高;生物油气化所得气体为中热值气体。     

氯化苄双羰化反应催化剂的研究

苯丙酮酸是合成苯丙氨酸的重要中间体 ,也是重要的动物新陈代谢产物 ,在生物化学和药物学上都有广泛的用途 .例如 ,在泌尿系统疾病的治疗中 ,摄入苯丙酮酸盐 ,可以在酶的作用下 ,结合体内过多的氨生成苯丙氨酸 ,从而降低血氨浓度 ,防止氨中毒 .合成苯丙酮酸的氯化苄双羰化方法应用较广 ,催化剂一般采用钴的配合物如八羰基二钴等 .这种方法一步完成 ,工艺简单 ,产品易分离、收率高 ,与传统的合成方法相比具有很大的优势 [1] .但催化剂八羰基二钴价格比较高 ,且在空气中不稳定 [2 ] .若能实现催化剂的回收再利用 ,对于实现苯丙酮酸的工业化生…