Total synthesis of (±)-paroxetine by diastereoconvergent cobalt-catalysed arylation

A total synthesis of paroxetine is reported, with a diastereoselective and diastereoconvergent cobalt-catalysed sp3–sp2 coupling reaction involving a 3-substituted 4-bromo-N-Boc-piperidine (Boc = tert-butoxycarbonyl) substrate as a key step. A 9:1 diastereoselectivity was obtained, while a control experiment involving a conformationally locked 3-substituted 4-bromo-tert-butyl cyclohexane ring proceeded with essentially complete stereoselectivit

The synthesis of mono- and difluorinated 2,3-dideoxy-d-glucopyranoses

The synthesis of 2,3-dideoxy-2,3-difluoro-d-glucose and 2,3-dideoxy-3-fluoro-d-glucose is reported in, respectively, 5 and 6 steps from d-glucal, using a fluorination strategy

The synthesis of tetrafluorinated aminosugars

The synthesis of two tetrafluorinated 4-aminosugars, 4-amino-2,3,4-trideoxy-2,2,3,3-tetrafluoro-d-erythro-hexopyranose hydrochloride (7•HCl) and 4-amino-2,3,4-trideoxy-2,2,3,3-tetrafluoro-d-threo-hexopyranose hydrochloride (8•HCl), is described. The amino group in ?-position of a CF2(CF2) group is proposed as a mimic for the hydrogen bond accepting capacity of an alcohol group in an unfluorinated sugar. The synthesis of the two sugars was achieved in 4 steps each from the sulfinylimine diastereoisomers of d-glyceraldehyde

Digital Templating and Preoperative Deformity Analysis with Standard Imaging Software

Analysis of deformity and subsequent correction are the basis for many orthopaedic surgical procedures. In advanced cases of joint degeneration, arthroplasty may be the only available treatment option. Until recently, these analyses and preoperative surgical plans have been performed using standard radiographs, tracing paper, and/or plastic overlays. Numerous customized, commercially available, computer-based preoperative planning software programs have been introduced. The purposes of this study were to describe (1) the techniques used in deformity analysis and preoperative surgical planning using standard radiographs for joint arthroplasty and corrective osteotomies of the extremities, (2) the use of computed tomography (CT) scans to analyze rotational deformities in the presence and absence of joint prostheses and in planning corrective rotational osteotomies or revision joint replacement, and (3) the techniques for analyzing angular deformities of the spine. All these applications were performed with a widely available image analysis software

Total synthesis of (–)-luminacin D

A second generation synthesis of (?)-luminacin D based on an early stage introduction of the trisubstituted epoxide group is reported, allowing access to the natural product in an improved yield and a reduced number of steps (5.4%, 17 steps vs 2.6%, 19 steps). A full account of the optimization work is provided, with the reversal of stereoselection in the formation of the C4 alcohol in equally excellent diastereoselectivity as key improvement

Investigating the influence of (Deoxy)fluorination on the lipophilicity of non-UV-active fluorinated alkanols and carbohydrates by a new log P determination method

Property tuning by fluorination is very effective for a number of purposes, and currently increasingly investigated for aliphatic compounds. An important application is lipophilicity (log?P) modulation. However, the determination of log?P is cumbersome for non-UV-active compounds. A new variation of the shake-flask log?P determination method is presented, enabling the measurement of log?P for fluorinated compounds with or without UV activity regardless of whether they are hydrophilic or lipophilic. No calibration curves or measurements of compound masses/aliquot volumes are required. With this method, the influence of fluorination on the lipophilicity of fluorinated aliphatic alcohols was determined, and the log?P values of fluorinated carbohydrates were measured. Interesting trends and changes, for example, for the dependence on relative stereochemistry, are reporte

Synthesis and conformational properties of 3,4-difluoro-L-prolines

Fluorinated proline derivatives have found diverse applications in areas ranging from medicinal chemistry over structural biochemistry to organocatalysis. Depending on the stereochemistry of monofluorination at the proline 3- or 4-position, different effects on the conformational properties of proline (ring pucker, cis/trans isomerization) are introduced. With fluorination at both 3- and 4-positions, matching or mismatching effects can occur depending on the relative stereochemistry. Here we report, in full, the syntheses and conformational properties of three out of the four possible 3,4-difluoro-L-proline diastereoisomers. The yet unreported conformational properties are described for (3S,4S)- and (3R,4R)-difluoro-L-proline, which are shown to bias ring pucker and cis/trans ratios on the same order of magnitude as their respective monofluorinated progenitors, although with significantly faster amide cis/trans isomerization rates. The reported analogues thus expand the scope of available fluorinated proline analogues as tools to tailor proline's distinct conformational and dynamical properties, allowing for the interrogation of its role in, for instance, protein stability or folding

Treating clinical mastitis in dairy cows with essential oils

Clinical mastitis is the main concern in dairy farming today, but there are very few drugs that are compatible with organic specifications. Our study was conducted in order to evaluate the therapeutic efficiency of the intramammary infusion of three essential oils, Thymus vulgaris, Rosmarinus verbenone and Laurus nobilis. Fifty-five cases of mastitis were treated with 10 ml of a mixture of the three oils (1.5% each in sunflower oil). Forty-five others were treated with 10 ml of a mixture of Thymus vulgaris and Rosmarinus verbenone (6% of each in sunflower oil or in water). The recovery rate was only 40%, which is deemed unsatisfactory

The adsorption and decomposition of carbon monoxide on Ni(100) and the oxidation of the surface carbide by oxygen

The interaction of carbon monoxide with Ni(100) has been studied by ellipsometry and Auger electron spectroscopy. Bombardment by electrons of a relatively high energy (2500 eV) leads to the disproportionation of the adsorbed CO (2 COad → Cad + CO2g ). The rate of oxidation of this surface carbide is , where hc is the carbon 272 eV Auger peak height, n=0.5 and the apparent activation energy Eact =13.3 kcal/mole. This relation is valid at 200–400°C and at oxygen pressures of 5 × 10−9−8 × 10−7 Torr