It was shown that the catalytic hydrogenation of α‐iminophosphonates by molecular hydrogen can serve as a convenient method for the synthesis of racemic and optically active α‐aminophosphonates. Up to 94% ee was achieved in the rhodium‐catalyzed enantioselective hydrogenation using chiral ligand (R)‐BINAP. 相似文献
A versatile keto ester reductase CgKR1, exhibiting a broad substrate spectrum, was obtained from Candida glabrata by genome data mining. It showed the highest activity toward an aliphatic β‐keto ester, ethyl 4‐chloro‐3‐oxobutanoate (COBE), but much lower activity toward bulkier α‐keto esters with an aromatic group, such as methyl ortho‐chlorobenzoylformate (CBFM) and ethyl 2‐oxo‐4‐phenylbutyrate (OPBE). By rational design of the active pocket, the substrate specificity of the reductase was significantly altered and this tailor‐made reductase showed a much higher activity toward aromatic α‐keto esters (∼7‐fold increase in kcat/Km toward CBFM) and lower activity toward aliphatic keto esters (∼12‐fold decrease in kcat/Km toward COBE). Meanwhile, the thermostability of the reductase was enhanced by a consensus approach. Such improvements may yield practical catalysts for the asymmetric bioreduction of these aromatic α‐keto esters
The polymer-supported bimetallic catalyst system PVP–PdCl2–CuCl2/PPh3 has good conversion and regioselectivity to carbonylation of α-(6′-methoxy-2′-naphthyl)ethanol under mild conditions. The effects of temperature, CO pressure, reaction time and P/Pd ratio have been studied to obtain optimum reaction conditions. The carbonylation of various α-arylethanols and styrene derivatives are also investigated with the same catalyst. X-ray photoelectron spectroscopy (XPS) and transmission electron micrograph (TEM) show that the polymer would protect palladium particles against aggregation and serve as a ligand. 相似文献
For the first time a mild and efficient procedure has been developed for the C‐3 selective ring opening, under biomimetic conditions, of 2,3‐aziridino alcohols and their derivatives with nucleophiles such as aromatic thiols and amines catalyzed by β‐cyclodextrin in water at room temperature to afford the corresponding β‐amino sulfides and diamines with high regioselectivity in impressive yields. The use of cyclodextrin precludes the use of either acid or base and the catalyst can be recovered and reused. 相似文献
A detailed commercial process for the synthesis and purification of the activated disaccharide, α-D -cellobiosyl bromide heptaacetate ( 1 ) was developed. Reaction of α-D -cellobiose octaacetate (CBO) with HBr in glacial acetic acid or in glacial acetic acid/methylene chloride combination affords α-D -cellobiosyl bromide heptaacetate in high yield and excellent quality. Process variables such as reaction solvent, reaction time, reaction temperature, HBr stoichiometry, isolation methods and product purification options were optimized for large-scale synthesis. α-D -Cellobiosyl bromide heptaacetate was successfully prepared in a commercial manufacturing plant. 相似文献
An efficient and generally applicable protocol for decarboxylative coupling of α,α‐difluoroarylacetic acids with ethynylbenziodoxolone (EBX) reagents has been developed, affording α,α‐difluoromethylated alkynes bearing various functional groups in moderate to excellent yields. Remarkably, this potassium persulfate (K2S2O8)‐promoted reaction employs water as solvent under transition metal‐free conditions, thus providing a green synthetic approach to α,α‐difluoromethylated alkynes.
A method for the preparation of 11α‐hydroxy derivatives of lithocholic and chenodeoxycholic acids, recently discovered to be natural bile acids, is described. The principal reactions involved were (1) elimination of the 12α‐mesyloxy group of the methyl esters of 3α‐acetate‐12α‐mesylate and 3α,7α‐diacetate‐12α‐mesylate derivatives of deoxycholic acid and cholic acid with potassium acetate/hexamethylphosphoramide; (2) simultaneous reduction/hydrolysis of the resulting △11‐3α‐acetoxy and △11‐3α,7α‐diacetoxy methyl esters with lithium aluminum hydride; (3) stereoselective 11α‐hydroxylation of the △11‐3α,24‐diol and △11‐3α,7α,24‐triol intermediates with B2H6/tetrahydrofuran (THF); and (4) selective oxidation at C‐24 of the resulting 3α,11α,24‐triol and 3α,7α,11α,24‐tetrol to the corresponding C‐24 carboxylic acids with NaClO2 catalyzed by 2,2,6,6‐tetramethylpiperidine 1‐oxyl free radical (TEMPO) and NaClO. In summary, 3α,11α‐dihydroxy‐5β‐cholan‐24‐oic acid and 3α,7α,11α‐trihydroxy‐5β‐cholan‐24‐oic acid have been synthesized and their nuclear magnetic resonance (NMR) spectra characterized. These compounds are now available as reference standards to be used in biliary bile acid analysis. 相似文献
Oxidative stress has been implicated as an important contributing factor in the pathogenesis of several pulmonary inflammatory diseases. Previous studies have indicated a relationship between oxidative stress and the attenuation of epithelial tight junctions (TJs). In Human Bronchial Epithelial-16 cells (16HBE), we demonstrated the degradation of zonula occludens-1 (ZO-1), and claudin-2 exhibited a great dependence on the activation of the transient receptor potential melastatin (TRPM) 2 channel, phospholipase Cγ1 (PLCγ1) and the protein kinase Cα (PKCα) signaling cascade. 相似文献
The hydrogenation of trans,4-phenyl,3-buten,2-one (benzalacetone) and trans,3-phenyl, propenal (cinnamaldehyde) was carried out on Au supported on iron oxides catalysts. Commercial goethite (FeOOH), maghemite (γFe2O3) and hematite (αFe2O3) were used as supports. The catalytic activity of Au/Fe2O3 reference catalyst, supplied by the World Gold Council, was also investigated. Gold catalysts and the parent supports were characterized by BET, X-ray diffraction (XRD), temperature programmed reduction (TPR), temperature programmed desorption of ammonia (NH3-TPD) and high resolution transmission electron microscopy (HRTEM).Among the catalysts investigated Au supported on FeOOH shows the highest activity and selectivity to UA in the hydrogenation of unsaturated carbonyl compounds whereas Au supported on αFe2O3 are the less active and selective catalysts.The catalytic activity and selectivity to unsaturated alcohols (UA) in the hydrogenation of benzalacetone and cinnamaldehyde are less influenced by the morphology of gold particles and are mainly influenced by the nature of the support.A correlation between the reducibility of the catalysts and the activity and selectivity to UA has been found. Increasing the reducibility of the catalysts both the activity and selectivity to UA increase. These results let us to argue that active and selective sites are formed by negative gold particles formed through the electron transfer from the reduced support to the metal. 相似文献
A method of correlating the value of the melting point of triacylglycerol (tag) with the values of the melting points of the three fatty acids constituting the tag as its acyl radicals was studied by applying the least squares method. The method was applied to the sets of values of the melting points of the α, β', and β forms of crystals of tag with saturated acyl radicals comprising decanoyl, lauroyl, myristoyl, palmitoyl, and stearoyl. The value of the melting point of the crystal form of the tag is expressed by prediction equations that comprise the values of the melting points of the three fatty acids above as variables. The best‐fit equation can be fixed by satisfying the criterion of least squares to the prediction equations. The method enables us to estimate the values of the melting points of possible molecular species of tag consisting of the acyl radicals above. The correlation coefficient relevant to the correlation between the values of the melting points of the particular crystal form and the corresponding values of the best‐fit equation is obtained. The more thermodynamically stable the crystal form, the larger is the value of the correlation coefficient. 相似文献
Nanocrystalline magnesium oxide was found to be an effective heterogeneous, solid base catalyst for the one‐pot Wittig reaction to afford α,β‐unsaturated esters and nitriles in excellent yields with high E‐stereoselectivity in the presence of triphenylphosphine under mild conditions. 相似文献
An efficient strategy for a high‐yielding and stereoselective synthesis of α‐trifluoromethyl unsaturated carboxylic acids directly from the reactions of 3,3,3‐trifluoropropanoic acid (CF3CH2COOH) with various aryl aldehydes in the presence of titanium tetrachloride (TiCl4) is reported here for the first time, which is a valuable expansion for the classical Knoevenagel reaction. Because these compounds may have potential applications in organic electronics and can be easily converted to the corresponding fluorinated alcohols and amino acids with excellent bioactivity, this route should be a good choice for the preparation of α‐trifluoromethyl‐containing derivatives. 相似文献
Direct targeting of intracellular Gα subunits of G protein‐coupled receptors by chemical tools is a challenging task in current pharmacological studies and in the development of novel therapeutic approaches. In this study we analyzed novel FR900359‐based analogs from natural sources, synthetic cyclic peptides, as well as all so‐far known Gqα inhibitors in a comprehensive study to devise a strategy for the elucidation of characteristics that determine interactions with and inhibition of Gq in the specific FR/YM‐binding pocket. Using 2D NMR spectroscopy and molecular docking we identified unique features in the macrocyclic structures responsible for binding to the target protein correlating with inhibitory activity. While all novel compounds were devoid of effects on Gi and Gs proteins, no inhibitor surpassed the biological activity of FR. This raises the question of whether depsipeptides such as FR already represent valuable chemical tools for specific inhibition of Gq and, at the same time, are suitable natural lead structures for the development of novel compounds to target Gα subunits other than Gq. 相似文献
Lipid deposition in artery walls is implied in the pathogenesis of atherosclerosis and imbalance between uptake and efflux of cholesterol favors the deposition. We investigated the effect of vitamin E with the same dose and duration on the different stages of atherosclerosis in Apolipoprotein E knockout (ApoE KO) mice and explored the potential mechanisms. The results showed that the ApoE KO mouse spontaneously develops atherosclerosis in an age‐dependent manner from 14 to 46 weeks on the regular chow. Vitamin E (100 mg/kg) supplementation to ApoE KO mice at 6, 14, and 22 weeks for 8 weeks significantly reduced the atherosclerotic lesion area by 41, 29 and 19 % respectively compared to the age‐matched control mice; however had no significant effect on the lesion when given at 30 and 38 weeks. In addition, vitamin E supplemented at the ages from 6 to 30 weeks decreased the contents of serum oxLDL and TBARS without affecting the TC and TAG contents in serum and liver. Furthermore, vitamin E supplemented at 6, 14 and 22 weeks down‐regulated vasculature mRNA expressions of scavenger receptor CD36 and up‐regulated mRNA expressions of PPARγ, LXRα and ABCA1 which are involved in reverse cholesterol transportation; however had no significant effects on these genes when given at 30 and 38 weeks. In conclusion, vitamin E with same dose and duration inhibits the early but not advanced atherosclerotic lesion in ApoE KO mice by anti‐oxidation and regulation of mRNA expression of genes involved in cholesterol uptake and efflux, which favors the improvement of atherosclerosis. 相似文献
Chiral auxiliary methodology and chiral assays have been developed to establish the enantiomeric purities of erythrulose and 1,3‐dihydroxypentan‐2‐one generated using wild‐type (WT) Escherichia coli transketolase (TK). L ‐Erythrulose was formed in 95% ee and (3S)‐1,3‐dihydroxypentan‐2‐one in 58% ee. Since the latter compound was formed in moderate ee, TK libraries were screened to identify higher performing mutants. A colorimetric screen and chiral assay were successfully applied to a 96‐well format, and new active TK mutants were identified, which gave 1,3‐dihydroxypentan‐2‐one in high stereoselectivities. Remarkably, active‐site single‐point mutants were identified that were able to both enhance and reverse the stereoselectivity of TK. 相似文献