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81.
Quentin Ronzon Dr. Wei Zhang Dr. Nicolas Casaretto Dr. Elisabeth Mouray Prof. Dr. Isabelle Florent Dr. Bastien Nay 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(28):7764-7772
The introduction of substituents on bare heterocyclic scaffolds can selectively be achieved by directed C−H functionalization. However, such methods have only occasionally been used, in an iterative manner, to decorate various positions of a medicinal scaffold to build chemical libraries. We herein report the multiple, site selective, metal-catalyzed C−H functionalization of a “programmed” 4-hydroxyquinoline. This medicinally privileged template indeed possesses multiple reactive sites for diversity-oriented functionalization, of which four were targeted. The C-2 and C-8 decorations were directed by an N-oxide, before taking benefit of an O-carbamoyl protection at C-4 to perform a Fries rearrangement and install a carboxamide at C-3. This also released the carbonyl group of 4-quinolones, the ultimate directing group to functionalize position 5. Our study highlights the power of multiple C−H functionalization to generate diversity in a biologically relevant library, after showing its strong antimalarial potential. 相似文献
82.
Dr. Aurélien Adenot Dr. Lucile Anthore-Dalion Dr. Emmanuel Nicolas Jean-Claude Berthet Dr. Pierre Thuéry Dr. Thibault Cantat 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(72):18047-18053
An air-tolerant Cu-catalyzed sulfonylative Hiyama cross-coupling reaction enabling the formation of diaryl sulfones is described. Starting from aryl silanes, DABSO and aryliodides, the reaction tolerates a large variety of polar functional groups (amines, ketones, esters, aldehydes). Control experiments coupled with DFT calculations shed light on the mechanism, characterized by the formation of a Cu(I)-sulfinate intermediate via fast insertion of a SO2 molecule. 相似文献
83.
Dustin T. Savage Nicolas J. Briot J. Zach Hilt Thomas D. Dziubla 《Journal of polymer science. Part A, Polymer chemistry》2021,59(4):289-299
Per- and polyfluoroalkyl substances (PFAS) have rapidly accumulated in the environment due to their widespread use prior to commercial discussion in the early 21st century, and their slow degradation has magnified concerns of their potential toxicity. Monitoring their distribution is, therefore, necessary to evaluate and control their impact on the health of exposed populations. This investigation evaluates the capability of a simple polymeric detection scheme for PFAS based on crosslinked, thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) hydrogels. Surveying swelling perturbations induced by several hydrotropes and comparable hydrocarbon analogs, tetraethylammonium perfluorooctane sulfonate (TPFOS) showed a significantly higher swelling ratio on a mass basis (65.5 ± 8.8 at 15°C) than any of the other analytes tested. Combining swelling with the fluorimetric response of a solvachromatic dye, nile red, revealed the fluorosurfactant to initiate observable aggregation (i.e., its critical aggregation concentration) at 0.05 mM and reach saturation (i.e., its charge neutralization concentration) at 0.5 mM. The fluorosurfactant was found to homogeneously distribute throughout the polymer matrix with energy dispersive X-ray spectroscopy, marking the swelling response as a peculiar nexus of fluorinated interfacial positioning and delocalized electrostatic repulsion. Results from the current study hold promise for exploiting the physiochemical response of PNIPAM to assess TPFOS's concentration. 相似文献
84.
Nicolas P. Cheval Barbara Hoffmann Anna Dikova Fatih Sirindil Philippe Bertus Aurélien Blanc Jean-Marc Weibel Patrick Pale 《Tetrahedron》2018,74(50):7111-7119
Vinyl nosylates, readily obtained from β-dicarbonyl derivatives, could be efficiently engaged in Sonogashira cross-coupling reactions, either cocatalyzed by copper or silver salts. The para-nitrobenzenesulfonate (nosylate) group allows this coupling to be performed under very mild conditions (room temperature). These new leaving group and mild conditions could be applied to the synthesis of acetylenic coumarinyl derivatives and to the total synthesis of an acetylenic monoterpene natural product, named cleviolide. 相似文献
85.
Bimetallic Gold(I) Complexes with Ethynyl‐Helicene and Bis‐Phosphole Ligands: Understanding the Role of Aurophilic Interactions in their Chiroptical Properties 下载免费PDF全文
Dr. Mehdi El Sayed Moussa Dr. Hui Chen Zuoyong Wang Dr. Monika Srebro‐Hooper Dr. Nicolas Vanthuyne Dr. Soizic Chevance Prof. Christian Roussel Prof. J. A. Gareth Williams Prof. Jochen Autschbach Prof. Régis Réau Prof. Zheng Duan Dr. Christophe Lescop Dr. Jeanne Crassous 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(17):6075-6086
Monometallic gold(I)‐alkynyl‐helicene complexes ( 1 a , b ) and bimetallic gold(I)‐alkynyl‐helicene architectures featuring the presence ( 2 a , b ) or absence ( 3 a , b ) of aurophilic intramolecular interactions were prepared by using different types of phosphole ligands (mono‐phosphole L1 or bis‐phospholes L2 , 3 ). The influence of the AuI d10 metal center(s) on the electronic, photophysical, and chiroptical properties of these unprecedented phosphole‐gold(I)‐alkynyl‐helicene complexes was examined. Experimental and theoretical results highlight the importance of ligand‐to‐ligand‐type charge transfers and the strong effect of the presence or absence of AuI–AuI interactions in 2 a , b . 相似文献
86.
Mathieu Gaudin Maï Panchal Sophie Ayciriex Erwan Werner Alain Brunelle David Touboul Claire Boursier‐Neyret Nicolas Auzeil Bernard Walther Charles Duyckaerts Olivier Laprévote 《Journal of mass spectrometry : JMS》2014,49(10):1035-1042
The development of ‘omics’ sciences offers new opportunities for the study of neurodegenerative diseases but increases at the same time the sample demand on brain banks that collect and store valuable human post‐mortem tissue. Our study aims to evaluate in lipidomics the potential of formalin‐fixed tissue compared with the cryopreservation method, considered as the gold standard for biochemical research. Two complementary liquid chromatography/mass spectrometry analytical platforms were used on the basis of hybrid quadrupole time‐of‐flight and triple quadrupole mass spectrometers. Untargeted fingerprinting, semitargeted profiling of specific lipid classes and targeted monitoring of lipid species were performed in formalin‐fixed and cryopreserved samples to provide detailed information at the molecular level on the formalin‐induced alterations of the brain tissue. In vitro incubations of lipid standards were also performed to further describe the degradation processes induced by formaldehyde. Phospholipid compounds were found to be extensively hydrolysed, whilst the sphingolipid ones were preserved. N‐methylation and N‐formylation of amine‐containing phospholipids have also been evidenced. These findings show that the potential detrimental effect of formalin on the analytes of interest must be taken into account when analysing formalin‐fixed samples. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
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