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21.
Lipiao Bao Baolin Zhao Vicent Lloret Marcus Halik Frank Hauke Andreas Hirsch 《Angewandte Chemie (International ed. in English)》2020,59(17):6700-6705
Patterned functionalization can, on the one hand, open the band gap of graphene and, on the other hand, program demanding designs on graphene. The functionalization technique is essential for graphene‐based nanoarchitectures. A new and highly efficient method was applied to obtain patterned functionalization on graphene by mild fluorination with spatially arranged AgF arrays on the structured substrate. Scanning Raman spectroscopy (SRS) and scanning electron microscopy coupled with energy‐dispersive X‐ray spectroscopy (SEM‐EDS) were used to characterize the functionalized materials. For the first time, chemical patterning on the bottom side of graphene was realized. The chemical nature of the patterned functionalization was determined to be the ditopic scenario with fluorine atoms occupying the bottom side and moieties, such as oxygen‐containing groups or hydrogen atoms, binding on the top side, which provides information about the mechanism of the fluorination process. Our strategy can be conceptually extended to pattern other functionalities by using other reactants. Bottom‐side patterned functionalization enables utilization of the top side of a material, thereby opening up the possibilities for applications in graphene‐based devices. 相似文献
22.
In this communication,we disclose the first example of metal-free and site-selective radical fluorination of readily available tertiary alkyl ethers,enabled by synergistic photocatalysis and organocatalysis.This catalytic combination allows for exclusive fluorination of tertiary C–O bonds under mild conditions even in the presence of competing reaction sites.The excellent functional group tolerance affords valuable access to sterically hindered alkyl fluorides through late-stage modification of complex molecules.The successful use of tertiary alkyl ethers in radical fluorination enhances the structural diversity of aliphatic fluorides that can be derived from naturally abundant alcohols. 相似文献
23.
Yurii A. Serguchev Maxim V. Ponomarenko Lyudmila F. Lourie Andrey A. Fokin 《Journal of Physical Organic Chemistry》2011,24(5):407-413
The addition of 1‐chloromethyl‐4‐fluoro‐1,4‐diazoniabicyclo[2.2.2]octane bis‐tetrafluoroborate (F‐TEDA) to unsaturated systems was modelled computationally at the ab initio levels and studied experimentally. The reaction of olefins with F‐TEDA is driven exclusively by charge transfer and displays the antibonding orbital picture in the transition structure for F‐transfer, similarly to that for the reactions of olefins with F‐radical. In contrast, the electrophilic and concerted fluorinations, respectively with H2O???F+ complex and with F2, show strong bonding interactions between the fluorine and olefin moieties in the transition structures. The reaction with F‐TEDA involves an initial formation of highly delocalized charge‐transfer complexes in the first step with further low‐barrier (ca 4 kcal) migration of fluorine and is best described as an inner‐sphere electron transfer. This nonelectrophilic mechanism is operative for the transannular addition of F‐TEDA to 3‐methylene‐7‐ethylidenebicyclo[3.3.1]nonane studied experimentally. The addition mode is determined by the formation of a more stable complex via the ethylidene fragment and demonstrates selectivities that differ from conventional electrophilic additions. This mechanistic scenario may be extended to the fluorination with xenon difluoride where similar products are formed in high yields. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
24.
Catalytic and Asymmetric Fluorolactonisations of Carboxylic Acids through Anion Phase Transfer 下载免费PDF全文
Dr. Dixit Parmar Dr. Modhu Sudan Maji Prof. Dr. Magnus Rueping 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(1):83-86
Catalytic fluorolactonisations of aromatic carboxylic acids have been developed. The reactions proceed under mild conditions using the commercially available reagent Selectfluor. A weak phase transfer of the reagent mediated by Na2CO3 allows the reaction to be conducted in non‐polar solvents. Furthermore, by the use of a catalytic amount of (DHQ)2PHAL (hydroquinine 1,4‐phthalazinediyl diether), the first asymmetric fluorolactonisation has been achieved. The corresponding isobenzofuran core can be found in many biologically active molecules. 相似文献
25.
Recent Progress in Direct Introduction of Fluorinated Groups on Alkenes and Alkynes by means of CH Bond Functionalization 下载免费PDF全文
Dr. Tatiana Besset Dr. Thomas Poisson Prof. Xavier Pannecoucke 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(51):16830-16845
The direct introduction of fluorine and fluorinated building blocks has recently attracted a lot of attention and particularly the direct functionalization of alkenes and alkynes. This review will highlight the major progress recently made in that field, with a focus on photocatalyzed transformations, base‐promoted processes, and transition metal‐catalyzed functionalization of alkenes and alkynes. Special attention will be paid to explanations of the reaction mechanisms. 相似文献
26.
T.M. Rangarajan D. Velayutham M. Noel R.P. Singh 《Journal of fluorine chemistry》2011,132(2):107-7021
The partially fluorinated HF soluble intermediates formed during the electrochemical perfluorination of propionyl chloride (PC) and n-butyryl chloride (n-BC) were analyzed after passing 0%, 25%, 50%, 75% and 100% of theoretical charge required for the fluorination of PC and n-BC. The acid fluorides formed were converted to their corresponding sodium salt by alkali treatment and were separated by methanol extraction. The methanol was subsequently removed from the extract by vacuum distillation and the residue containing partially fluorinated sodium carboxylates was analyzed using 19F and 1H NMR spectra. Initial perfluorination on activated electrode surface indicates the operation of ‘zipper-mechanism’. Formation of partially fluorinated product mixture, initial selectivity towards primary and secondary carbon, carbon chain isomerization and formation of cleaved and coupled products support the general operation of free radical pathway in the overall electrochemical process. 相似文献
27.
A convenient, five‐step preparation of 2‐acetyl‐4,5‐difluorothiophene from 2,3‐dibromothiophene is described. 相似文献
28.
29.
Richard D. Chambers Takashi Okazoe Emmanuelle Thomas 《Journal of fluorine chemistry》2010,131(9):933-936
Reactions of dialkyl ethers with either fluorine or Selectfluor™ led to the formation of unusual difluorinated polyether products in modest yields. A mechanism involving initial fluorination of the site adjacent to ether oxygen followed by elimination of hydrogen fluoride, reaction of the generated enol system with a further equivalent of fluorinating agent giving an oxonium system which reacts with water during aqueous work-up to lead eventually to the products observed, is suggested. 相似文献
30.