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Asymmetric synthesis of 1,3-oxathiolan-5-one derivatives through dynamic covalent kinetic resolution
The asymmetric synthesis of 1,3-oxathiolan-5-one derivatives through an enzyme-catalyzed, dynamic covalent kinetic resolution strategy is presented. Dynamic hemithioacetal formation combined with intramolecular, lipase-catalyzed lactonization resulted in good conversions with moderate to good enantiomeric excess (ee) for the final products. The process was evaluated for different lipase preparations, solvents, bases, and reaction temperatures, where lipase B from Candida antarctica (CAL-B) proved most efficient. The substrate scope was furthermore explored for a range of aldehyde structures, together with the potential access to nucleoside analog inhibitor core structures. 相似文献
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Francęois D. Tropper Fredrik O. Andersson Suoding Cao René Roy 《Journal of carbohydrate chemistry》2013,32(6):741-750
Abstract Peracetylated glycosyl- and glycobiosyl bromides and chlorides 1-4 including acetochloroneuraminic acid 5 were stereoselectively transformed into their corresponding S-glycosyl xanthates 6-10 in high yield (91-98%) under phase transfer catalyzed conditions. The reactions occurred at room temperature using tetrabutylammonium hydrogen sulfate as the catalyst. The substitutions gave complete inversion of configuration and thus proceeded by an SN2 type mechanism. Changing the organic solvent from methylene chloride to ethyl acetate had no detrimental effect on the outcome of the reactions but avoided an undesirable side reaction between the xanthate anion and methylene chloride. 相似文献
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Björn Johansson Prof. Fredrik Höök Prof. David Klenerman Dr. Peter Jönsson 《Chemphyschem》2014,15(3):486-491
An important and characteristic property of a cell membrane is the lateral mobility of protein molecules in the lipid bilayer. This has conventionally been measured by labeling the molecules with fluorescent markers and monitoring their mobility by different fluorescence‐based techniques. However, adding the label to the studied molecule may affect the system, so it is an assumption in almost all experiments that the measured mobility of the biomolecule with its label is the same as that of the unlabeled molecule. However, this assumption is rarely tested due to a lack of suitable methods. In this work, a new technique to perform label‐free diffusivity measurements is developed and used to measure the effect of the label for two common protein–lipid systems: 1) streptavidin (SA) coupled to a supported lipid bilayer (SLB) through biotinylated lipids and 2) the extracellular part of the T‐cell adhesion protein CD2, coupled to an SLB through histidine tags to nickel‐chelating lipids. A measurable (≈12 %) decrease in diffusivity is found for both labeled proteins, even though the molecular mass of the label is almost 100 times smaller than those of the proteins (≈50 kDa). The results illustrate the importance of being able to study different biophysical properties of cell membranes and their mimics without relying on fluorescent labels, especially if fluorescent labeling is difficult or is expected to affect the nature of the intermolecular interactions being studied. 相似文献
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Inside Back Cover: The Nature of Activated Non‐classical Hydrogen Bonds: A Case Study on Acetylcholinesterase–Ligand Complexes (Chem. Eur. J. 8/2016) 下载免费PDF全文
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A new method for the synthesis of allyl aromatic compounds not involving any metal-containing reagent or catalyst has been developed. Arylamines substituted with a large number of different substituents were converted via diazotizative deamination with tert-butyl nitrite in allyl bromide and acetonitrile to the corresponding allyl aromatic compounds. The allylation reaction was found to be suitable for larger scale synthesis due to short reaction times, a nonextractive workup, and robustness toward moisture, air, and type of solvent. 相似文献
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Broad Gaussian line shapes are observed in scanning tunneling spectroscopy of single, localized electronic states induced by Cl vacancies in ultrathin NaCl films on Cu surfaces. Using a simple inelastic resonance tunneling model, we show that the observed broad line shapes are caused by a strong coupling between the localized state and the optical phonons in the film. The parameters for the model are obtained from density functional calculations, in which the occupation of the vacancy state temporarily taking place in the experiment has also been accounted for. 相似文献