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1.
Dr. Christine Beemelmanns Dr. Dominik Nitsch Dr. Christoph Bentz Prof. Dr. Hans-Ulrich Reissig 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(37):8780-8789
A series of γ-indolylketones with fluorine, cyano or alkoxy substituents at the benzene moiety was prepared and subjected to samarium diiodide-promoted cyclization reactions. The desired dearomatizing ketyl cascade reaction forming two new rings proceeded in all cases with high diastereoselectivity, but with differing product distribution. In most cases, the desired annulated tetracyclic compounds were obtained in moderate to good yields, but as second product tetracyclic spirolactones were isolated in up to 29 % yield. The reaction rate was influenced by the substituents at the benzene moiety of the substrate as expected, with electron-accepting groups accelerating and electron-donating groups decelerating the cyclization process. In case of a difluoro-substituted γ-indolylketone a partial defluorination was observed. The intermediate samarium enolate of the tetracyclic products could be trapped by adding reactive alkylating agents as electrophiles delivering products with quarternary carbons. In the case of a dimethoxy-substituted tetracyclic cyclization product a subsequent reductive amination stereoselectively provided a pentacyclic compound that was subsequently N-protected and subjected to a regioselective elimination. The obtained functionalized pentacyclic product should be convertible into the alkaloid brucine by four well-established steps. Overall, the presented report shows that functionalized tetracyclic compounds with different substituents are rapidly available with the samarium diiodide cascade cyclization as crucial step. Hence, analogues of the landmark alkaloid strychnine, for example, with specific fluorine substitutions, should be easily accessible. 相似文献
2.
Wei Peng Jie Dong Han‐Bin Li Christine Chow Qiao‐Sheng Hu 《Journal of polymer science. Part A, Polymer chemistry》2019,57(14):1606-1611
Room temperature Suzuki cross‐coupling polymerization of aryl dibromides/diiodides with aryldiboronic acids/acid esters with t‐Bu3P‐coordinated 2‐phenylaniline‐based palladacycle complex, [2′‐(amino‐kN)[1,1′‐biphenyl]‐2‐yl‐kC]chloro(tri‐t‐butylphosphine)palladium, as a general precatalyst is described. Such room temperature Suzuki cross‐coupling polymerization is achieved by employing six equivalents or more of the base and affords polymers within an hour, with the yields and the molecular weights in general comparable to or higher than reported results that required higher reaction temperature and/or longer polymerization time. Our study provides a general catalyst system for the room temperature Suzuki cross‐coupling polymerization of aryl dibromides/diiodides with aryldiboronic acids/acid esters and paves the road for the investigation of employing other monodentate ligand‐coordinated palladacycle complexes including other electron‐rich monophosphine‐coordinated ones for room temperature cross‐coupling polymerizations. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1606–1611 相似文献
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Christine A. Bange Prof. Dr. Rory Waterman 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(36):12598-12605
Despite significant advances, metal‐catalyzed hydrophosphination has ample room for discovery, growth, and development. Many of the key successes in metal‐catalyzed hydrophosphination over the last decade have indicated what is needed and what is yet to come. Reactivity that is absent from the literature also speaks to the challenges in catalytic hydrophosphination. This Concept article discusses and highlights recent developments that address the ongoing challenges, and identifies areas in metal‐catalyzed hydrophosphination that are underdeveloped. Advances in product selectivity, catalyst design, and both unsaturated and phosphine substrates illustrate the ongoing development of the field. Like all catalytic transformations, the benefits are realized through catalyst, ligand, and conditions, and consideration of those features are the route to a yet more efficient and broadly applicable reaction. 相似文献
9.
Susan C. Scott Nicole M. Anders Ping He Avelina Hemingway Steven D. Gore Christine L. Hann Michelle A. Rudek 《Biomedical chromatography : BMC》2022,36(3):e5289
The Bcl-2 family small molecule inhibitor navitoclax is being clinically evaluated to treat multiple cancers including lymphoid malignancies and small cell lung cancer. A sensitive and reliable method was developed to quantitate navitoclax in human plasma using liquid chromatography with tandem mass spectrometry with which to perform detailed pharmacokinetic studies. Sample preparation involved protein precipitation using acetonitrile. Separation of navitoclax and the internal standard, navitoclax-d8, was achieved with a Waters Acquity UPLC BEH C18 column using isocratic flow over a 3 min total analytical run time. A SCIEX 4500 triple quadrupole mass spectrometer operated in positive electrospray ionization mode was used for the detection of navitoclax. The assay range was 5–5,000 ng/ml and proved to be accurate (89.5–104.9%) and precise (CV ≤ 11%). Long-term frozen plasma stability for navitoclax at −70°C was at least 43 months. The method was applied for the measurement of total plasma concentration of navitoclax in a patient receiving a 250 mg daily oral dose. 相似文献
10.
Silvia Rita Amato Aviva Burnstock Maureen Cross Koen Janssens Francesca Rosi Laura Cartechini Raffaella Fontana Alice Dal Fovo Marco Paolantoni Chiara Grazia Aldo Romani Anne Michelin Christine Andraud Aurélie Tournié Joris Dik 《X射线光谱测定》2019,48(4):282-292
The paintings by Édouard Manet in The Courtauld Gallery Déjeuner sur l'herbe (1863–68), Marguerite de Conflans en Toilette de Bal (1870–1880), Banks of the Seine at Argenteuil (1874), and A Bar at the Folies–Bergère (1882) were investigated for the first time using a range of non-invasive in situ analyses. The aims of the study were to investigate the painting techniques and materials used for this group of works and to critically evaluate the technical evidence derived from the integrated use of imaging techniques and portable spectroscopic methods in this context. The paintings were investigated by means of macro X-ray fluorescence (MA-XRF), reflection spectral imaging, portable UV–Vis–NIR spectroscopy, portable Raman spectroscopy, and reflection FTIR. MA-XRF and reflection spectral imaging allowed visualising elements in the compositions that were not visible using traditional methods of technical study. For example, MA-XRF analysis of Déjeuner sur l'herbe revealed elements of the development of the composition that provided new evidence to consider its relationship to other versions of the composition. The study also highlighted questions about the interpretation of elemental distribution maps and spectral images that did not correspond to the reworking visible in X-radiographs. For example, in A Bar at the Folies–Bergère Manet made numerous changes during painting, which were not clearly visualised with any of the techniques used. The research has wider implications for the study of Impressionist paintings, as the results will support technical studies of works by other artists of the period who used similar materials and painting methods. 相似文献