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131.
132.
Maude Aelterman Tony Biremond Prof. Dr. Philippe Jubault Prof. Dr. Thomas Poisson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(66):e202202194
The electrochemical synthesis of fluorinated allyl silanes and boronates was disclosed. The addition of electrogenerated boryl or silyl radicals onto many α-trifluoromethyl or α-difluoromethylstyrenes in an undivided cell allowed the formation of a large panel of synthetically useful gem-difluoro and γ-fluoroallyl boronates and silanes (64 examples, from 31 % to 95 % yield). In addition, a scale up of the reactions under continuous flow was showcased using an electrochemical reactor with promising volumetric productivity (688 g.L−1.h−1 and 496 g.L−1.h−1). Moreover, the synthetic utility of these building blocks was highlighted through versatile transformations. Finally, plausible reaction mechanisms were suggested to explain the formation of the products. 相似文献
133.
Poisson L Gloaguen E Mestdagh JM Soep B Gonzalez A Chergui M 《The journal of physical chemistry. A》2008,112(39):9200-9210
We report on microscopic observation of solvation by argon atoms of excited states of an ethylenic-like molecule, TDMAE (tetrakis dimethylaminoethylene). Two experimental methods were used: gas phase dynamics for the observation of the evolution through excited states, matrix isolation spectroscopy for characterization of the initial states. Excited state dynamics was recorded after the molecule had been deposited on the surface of a large argon cluster (n approximately 100) by pick-up. The deposited cluster was characterized by mass spectrometry and by its shifted photoelectron spectrum. The time evolution of the system was visualized by femtosecond pump/probe velocity map imaging of photoelectrons. The time evolution of deposited TDMAE excited at 266 nm can be modeled via a modified three state model, as in the free molecule. The initially excited state is of valence character, and a Rydberg state mediates the passage to a zwitterionic configuration. The specific solvation of Rydberg states by the surface of the cluster was directly observed and is discussed. It represents the striking outcome of the present work. It is inferred that differently from the gas phase, solvated Rydberg states resulting from state mixing within a R(n/lambda) complex in the presence of the argon surface are reached. Solvation of these Rydberg states should be effective through interaction of the ion core of the excited molecules with the cluster. 相似文献
134.
Alexander G. Volkov Jewel S. Hairston Gamaliel Taengwa Jade Roberts Lincoln Liburd Darayas Patel 《Molecules (Basel, Switzerland)》2022,27(20)
Cold atmospheric pressure plasma (CAPP) is widely used in medicine for the treatment of diseases and disinfection of bio-tissues due to its antibacterial, antiviral, and antifungal properties. In agriculture, CAPP accelerates the imbibition and germination of seeds and significantly increases plant productivity. Plasma is also used to fix molecular nitrogen. CAPP can produce reactive oxygen and nitrogen species (RONS). Plasma treatment of bio-tissue can lead to numerous side effects such as lipid peroxidation, genotoxic problems, and DNA damage. The mechanisms of occurring side effects when treating various organisms with cold plasma are unknown since RONS, UV-Vis light, and multicomponent biological tissues are simultaneously involved in a heterogeneous environment. Here, we found that CAPP can induce in vitro oxidation of the most common water-soluble redox compounds in living cells such as NADH, NADPH, and vitamin C at interfaces between air, CAPP, and water. CAPP is not capable of reducing NAD+ and 1,4-benzoquinone, despite the presence of free electrons in CAPP. Prolonged plasma treatment of aqueous solutions of vitamin C, 1,4-hydroquinone, and 1,4-benzoquinone respectively, leads to their decomposition. Studies of the mechanisms in plasma-induced processes can help to prevent side effects in medicine, agriculture, and food disinfection. 相似文献
135.
136.
Pauline Poutrel Maria V. Ivanova Prof. Dr. Xavier Pannecoucke Prof. Dr. Philippe Jubault Prof. Dr. Thomas Poisson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(67):15262-15266
The catalytic asymmetric synthesis of β-trifluoromethylated esters or nitriles is reported. The use of an in situ formed chiral Cu−H complex allowed the enantioselective reduction of β-trifluoromethylated acrylates or acrylonitriles. The reaction proceeds smoothly affording the corresponding enantioenriched products in good to excellent yields and outstanding enantioselectivities (up to 98 % ee). The mechanism of the reaction was studied, and a plausible reaction pathway was suggested accordingly. Finally, the versatility of the products was highlighted through functional group manipulations. 相似文献
137.
Floriane Doche Dr. Julien Escudero Dr. Fabien Petit-Cancelier Dr. Heng-Ying Xiong Dr. Samuel Couve-Bonnaire Dr. Davide Audisio Prof. Dr. Thomas Poisson Dr. Tatiana Besset 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(64):e202202099
The unprecedented Pd-catalyzed (ethoxycarbonyl)difluoromethylthiolation reaction of various unsaturated derivatives was studied. In the presence of the (ethoxycarbonyl)difluoromethylsulfenamide reagent I and under mild reaction conditions (60 °C), both 2-(hetero)aryl and 2-(α-aryl-vinyl)pyridine derivatives were smoothly functionalized with this methodology (37 examples, up to 87 % yield). Moreover, the synthetic interest of this fluorinated moiety was further showcased by its conversion into various original fluorinated residues. Finally, a plausible mechanism for this transformation was suggested. 相似文献
138.
Amandine Pons Dr. Pavel Ivashkin Dr. Thomas Poisson Prof. Dr. André B. Charette Prof. Dr. Xavier Pannecoucke Prof. Dr. Philippe Jubault 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(18):6239-6242
A catalytic asymmetric synthesis of halocyclopropanes is described. The developed method is based on a carbenoid cyclopropanation of 2‐haloalkenes with tert‐butyl α‐cyano‐α‐diazoacetate using a chiral rhodium catalyst that permits access to a broad range of highly functionalized chiral halocyclopropanes (F, Cl, Br, and I) in good yields, moderate diastereoselectivity, and excellent enantiomeric ratios. The reported methodology represents the first general catalytic enantioselective approach to halocyclopropanes. 相似文献
139.
Herein, the straightforward C-3 functionalization of 4-dimethylaminopyridine (DMAP) backbone is disclosed. An efficient halogen-metal exchange procedure from 3-bromo DMAP 1 is reported providing a large panel of C-3 functionalized DMAPs. In addition, a Pd-catalysed C–N cross-coupling reaction is also described furnishing new 3-amino DMAPs. These new functionalization pathways led to the resolution-free synthesis of three new chiral DMAP catalysts in few steps and a good overall yield. These new catalysts were evaluated into the Steglich rearrangement giving modest enantioselectivities (up to 20% ee). 相似文献
140.