Stereoselective syntheses of highly functionalized bicyclo[3.1.0]hexanes: a general methodology for the synthesis of potent and selective mGluR2/3 agonists

[Chemical reaction: See text] A Et3Al mediated intramolecular epoxide opening, cyclopropanation reaction is described. The transformation provided highly functionalized bicyclo[3.1.0]hexane systems in high efficiency and with perfect H or F endo selectivity. Application of this reaction to the synthesis of mGluR2/3 agonist 1 (43% overall yield) and a few intermediates suitable for the synthesis of other bicyclo[3.1.0]hexane mGluR2/3 agonists is discussed.     

An efficient and scalable synthesis of substituted phenanthrenequinones by intramolecular Friedel-Crafts reaction of imidazolides

An efficient synthesis of 9,10-phenanthrenequinones is described. The two carbonyl groups were introduced by an orthoselective intermolecular Friedel-Crafts reaction of 3-methoxyphenol with ethyl chlorooxoacetate. The formation of a biaryl bond by Suzuki-Miyaura coupling reaction, followed by the hydrolysis of the ester, gave a biaryloxoacetic acid. Treatment of this acid with CDI gave the corresponding imidazolide. The ring closure to the desired phenanthrenequinone was accomplished by intramolecular Friedel-Crafts reaction of the imidazolide promoted by TiCl(4).     

Enantioselective syntheses of bicyclo[3.1.0]hexane carboxylic acid derivatives by intramolecular cyclopropanation

Enantioselective syntheses of bicyclo[3.1.0]hexane carboxylic acid derivatives are described. The syntheses were achieved by an intramolecular cyclopropanation as the key step, starting from enantiomerically pure starting materials that are commercially available.     

天山花楸果实中微量元素及氨基酸的检测分析

为探讨天山花楸果实中微量元素与药理学的相互关系,采用原子吸收分光光度仪和氨基酸自动分析仪分别测定了花楸果实中8种微量元素及17种氨基酸。结果表明,天山花楸果实中含有比较丰富的人体必需氨基酸及微量元素,它与天山花楸的临床保健作用有一定的相关性,具有很高的开发价值。     

Efficient synthesis of antiviral agent uprifosbuvir enabled by new synthetic methods

An efficient route to the HCV antiviral agent uprifosbuvir was developed in 5 steps from readily available uridine in 50% overall yield. This concise synthesis was achieved by development of several synthetic methods: (1) complexation-driven selective acyl migration/oxidation; (2) BSA-mediated cyclization to anhydrouridine; (3) hydrochlorination using FeCl₃/TMDSO; (4) dynamic stereoselective phosphoramidation using a chiral nucleophilic catalyst. The new route improves the yield of uprifosbuvir 50-fold over the previous manufacturing process and expands the tool set available for synthesis of antiviral nucleotides.

An efficient route to the HCV antiviral agent uprifosbuvir was developed in 5 steps from readily available uridine in 50% overall yield.     

The combustion reactivity of coal chars in oxyfuel atmosphere: Comparison of different random pore models

Recently the oxyfuel combustion of coal chars having a significant impact on reducing greenhouse emissions is gradually paid extensive attention by many researchers, but only a limited number of studies have focused on its reaction mechanism. Therefore, it is important to investigate the combustion mechanism of coal chars in oxyfuel atmosphere, while random pore model (RPM) is usually recommended as a model for the comprehensive simulation of coal chars reaction. In this context, the values of structure parameter ψ in RPM were calculated based on pore structural character at various carbon conversions, and show interesting evolution phenomena keeping constant at the preceding reaction stage before increasing remarkably at the end of stage. Consequently, a new model, two-stage random pore model (TRPM), was applied to the coal chars combustion in oxyfuel atmosphere. Compared to other models such as RPM, the Struis model (Model I), the Liu model (Model II), and fractal random pore model (FRPM), it shows that two-stage random pore model was more accurate to describe coal chars combustion under oxyfuel conditions, especially at higher carbon conversions. In addition, the oxyfuel combustion process of coal chars at 1323 K and 1373 K were analyzed.     

Efficient numerical methods for multiple surfactant-coated bubbles in a two-dimensional stokes flow

We present efficient and highly accurate numerical methods to compute the deformation of surfactant-coated, two-dimensional bubbles in a slow viscous flow. Surfactant acts to locally alter the surface tension and thereby change the nature of the interface motion. In this paper, we restrict our attention to the case of a dilute insoluble surfactant. The convection–diffusion equation for the surfactant concentration on the interface is coupled with the Stokes equations in the fluid domain through a boundary condition based on the Laplace-Young condition. The Stokes equations are first recast as an integral equation and then solved using a fast-multipole accelerated iterative procedure. The computational cost per time-step is only O(N log N) operations, with N being the number of discretization points on the interface. The bubble interfaces are described by a spectral mesh and is advected according to the fluid velocity in such a manner so as to preserve equal arc length spacing of marker points. This equal arc length framework has the dual advantage of dynamically maintaining the spatial mesh and allowing efficient, implicit treatment of the stiffest terms in the dynamics. Several phenomenologically different examples are presented.     

Practical synthesis of a highly functionalized thiazole ketone

Compound 1 is a uniquely substituted ketone prepared via addition of a thiazole anion to an aromatic nitrile in good overall yield. An exploration into the generality of the addition of thiazole anions to nitriles allowed us to make a variety of thiazole ketones in good to excellent yields. The non-odorous thiolate-mediated demethylation reaction used in the synthesis of 1 is also presented.