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Valerio Fasano Nils Winter Adam Noble Varinder K. Aggarwal 《Angewandte Chemie (International ed. in English)》2020,59(22):8502-8506
There is considerable interest in incorporating fluorine into agrochemicals and pharmaceuticals to improve their biological properties. Whilst a number of methods have been reported for installing CH2F and CHF2 groups, they are mainly limited to radical reactions, which are invariably racemic. Herein, we report the divergent, stereospecific reaction of fluoroiodomethyllithium with boronic esters to give α‐fluoro‐boronic esters. These unique intermediates can be readily transformed into the corresponding mono‐ or difluoromethylated compounds through proto‐ or fluorodeboronation, respectively. The use of the highly unstable fluoroiodomethyllithium was key to allowing rapid 1,2‐migration over competing decomposition of the carbanion. DFT calculations informed and supported the experimental findings. 相似文献
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Mariangela Lopreiato Rossana Cocchiola Susanna Falcucci Martina Leopizzi Michele Cardone Valeria Di Maio Umberto Brocco Valerio D'Orazi Stefano Calvieri Roberto Scandurra Federico De Marco Anna Scotto d'Abusco 《Photochemistry and photobiology》2020,96(1):74-82
The ultraviolet (UV) component of solar radiation is the driving force of life on earth, but it can cause photoaging and skin cancer. In this study, we investigated the effects of the glucosamine-derivative 2-(N-Acetyl)-L-phenylalanylamido-2-deoxy-β-D-glucose (NAPA) on human primary fibroblasts (FBs) stimulated in vitro with environmental levels of UVB radiation. FBs were irradiated with 0.04 J cm−2 UVB dose, which resulted a mild dosage as shown by the cell viability and ROS production measurement. This environmental UVB dose induced activation of MAP kinase ERK 1/2, the stimulation of c-fos and at lower extent of c-jun, and in turn AP-1-dependent up-regulation of pro-inflammatory factors IL-6 and IL-8 and suppression of collagen type I expression. On the contrary, 0.04 J cm−2 UVB dose was not able to stimulate metalloprotease production. NAPA treatment was able to suppress the up-regulation of IL-6 and IL-8 via the inhibition of MAP kinase ERK phosphorylation and the following AP-1 activation, and was able to attenuate the collagen type I down-regulation induced by the UVBs. Taken together, our results show that NAPA, considering its dual action on suppression of inflammation and stimulation of collagen type I production, represents an interesting candidate as a new photoprotective and photorepairing agents. 相似文献
376.
Valerio?Bertolasi Shasta?Lee?Mosher Keith?VaughanEmail author 《Journal of chemical crystallography》2005,35(2):119-124
1,4-Di-[2-phenyl-1-diazenyl]perhydro-1,4-diazepine (1) has been synthesized by reaction of benzenediazonium chloride with homopiperazine (perhydro-1,4-diazepine). The crystal structure of 1 has been determined by single crystal X-ray diffraction analysis. The bis-triazene (1) adopts an extended conformation which precludes any close intramolecular interaction of the phenyl rings. The heterocyclic seven-membered ring adopts a chair conformation, with the triazene side chains occupying alternate axial and equatorial positions consistent with cis-geometry. Internal torsion angles of the seven-membered ring have been measured. The crystal packing is determined by short contacts between C=H groups of phenyl rings and nitrogens of triazene moieties and by van der Waals interactions, with no evidence for intermolecular – interactions. This work establishes the structure of the product of diazonium coupling with homopiperazine as 1,4-di[(E)-2-phenyl-1-diazenyl]perhydro-1,4-diazepine. Crystal data: 1 C17H20N6, monoclinic, space group P21/n, a = 9.1838(5) Å, b = 12.1095(6) Å, c = 15.0081(8) Å, = 101.320(2), V = 1636.6(2) Å,3 for Z = 4. 相似文献
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Abstract The computer modelling technique was used in the present work to study the intrinsic defects and the migration processes in KY3F10. The main intrinsic disorder was found to be F Frenkel pairs but at higher temperatures it is possible that KF pseudo-Schottky defects could also be present in the material. The ionic conduction process is mainly due to the fluorine ions migrating via both vacancy and interstitialcy mechanisms. 相似文献
378.
In this work we are investigating dopant environments in LiYF 4 -LiREF 4 (RE=rare-earth cations) solid solutions, via EXAFS. The main aims are to identify the local environmental symmetry and the average lattice distortion as a function of the concentration and the type of the RE ion. LiY 1 m x RE x F 4 (RE=Gd or Lu) (0< x <1) single crystals were grown by the Czochralski technique under argon or CF 4 atmosphere, crystal-pulling rates were 0.6-1 v mm/h for <100>-oriented boules, with 8-25 v rpm rotation rates. Most of the crystals were also codoped with 2.7 v mol% of neodymium in the melt. EXAFS measurements were performed in transmission and fluorescence modes in the synchrotron XAS line of the LNLS, Campinas, Brazil, in and above the L III absorption edges of the RE ions. The samples were prepared as powder films, for the transmission mode measurements, and as powder or single crystals for fluorescence mode measurements. The WINXAS program was used for data reduction and fitting, and the FEFF6 package was used for the simulations of the spectra. The EXAFS oscillation curves were obtained by standard procedure. 相似文献
379.
Modulated Murrell-Shaw-Musher-Amos perturbation theory is used in second order to calculate the interaction energy between two ground-state hydrogen atoms in the region of intermediate internuclear separations from 0 to 6 bohr. Using a small set of variationally optimized two-electron functions accounting for the majority of induction and for spherical and dipole contributions to dispersion, fairly accurate results are obtained for the interaction over the whole range of distances including the united atom. A marked reduction in the induction energy is observed in short range when second-order exchange is introduced. 相似文献
380.