Polymerizations of perfluorinated vinyl ethers (PFVEs) provide an important category of fluoropolymers that have received considerable interests in applications. In this work, we report the development of an organocatalyzed controlled radical alternating terpolymerization of PFVEs and vinyl ethers (VEs) under visible-light irradiation. This method not only enables the synthesis of a broad scope of fluorinated terpolymers of low dispersities and high chain-end fidelity, facilitating tuning the chemical compositions by rationally choosing the type and/or ratio of comonomers, but also allows temporal control of chain-growth, as well as the preparation of a variety of novel fluorinated block copolymers. To showcase the versatility of this method, fluorinated alternating terpolymers have been synthesized and customized to simultaneously display a variety of desirable properties for solid polymer electrolyte design, creating new opportunities in high-performance energy storage devices.
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http://dx.doi.org/10.1002/anie.202107066 | DOI Listing |
J Org Chem
January 2025
Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati, Assam 781039, India.
The photoacid-catalyzed synthesis of 2-deoxy glycosides is presented using stable glycosyl -[1-(-MeO-Phenyl)vinyl]benzoate (PMPVB) donors and employing the eosin Y and diphenyl disulfide (PhSSPh) catalytic system in the presence of blue LED lights. The remote activation of the alkene functionality under the photoacid catalysis followed by a 5-- cyclization led to the generation of oxocarbenium ions that were trapped to provide the glycosylated products in excellent yields and decent selectivities under mild conditions. This method is also useful for the photoacid-catalyzed synthesis of -methoxybenzyl-alkyl ethers.
View Article and Find Full Text PDFACS Omega
December 2024
Division of Materials Science, Nara Institute of Science and Technology, 8916-5 Takayama-cho, Ikoma, Nara 630-0192, Japan.
A Hoveyda-Grubbs (HG)-type olefin metathesis complex with a selenoether moiety at the terminus of phenoxy moiety was synthesized. The complex showed direct selenium-atom coordination to the ruthenium center, resulting in higher thermodynamic stability compared with the parent HG catalyst. The selenium atom binding enhanced the tolerance to protic solvent molecules in ring-closing metathesis of -tosyldiallylamide and diethyl diallylmalonate, and also in the cross metathesis between 3-butenylbenzoate and methyl acrylate.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Laboratory of Catalysis and Organic Synthesis, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne, CH-1015, Lausanne, Switzerland.
The azidofunctionalization of alkenes under mild conditions using commercially available starting materials and easily accessible reagents is reported based on a radical-polar crossover strategy. A broad range of alkenes, including vinyl arenes, enamides, enol ethers, vinyl sulfides, and dehydroamino esters, were regioselectively functionalized with an azide and nucleophiles such as azoles, carboxylic acids, alcohols, phosphoric acids, oximes, and phenols. The method led to a more efficient synthesis of 1,2-azidofunctionalized pharmaceutical intermediates when compared to previous approaches, resulting in both reduction of step count and increase in overall yield.
View Article and Find Full Text PDFGels
December 2024
School of Chemistry and Materials Science, Guangdong University of Education, Guangzhou 510303, China.
Compared to traditional liquid electrolytes, solid electrolytes have received widespread attention due to their higher safety. In this work, a vinyl functionalized metal-organic framework porous material (MIL-101(Cr)-NH-Met, noted as MCN-M) is synthesized by postsynthetic modification. A novel three-dimensional hybrid gel composite solid electrolyte (GCSE-P/MCN-M) is successfully prepared via in situ gel reaction of a mixture containing multifunctional hybrid crosslinker (MCN-M), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), ethylene carbonate (EC), diethylene glycol monomethyl ether methacrylate (EGM) and polyethylene (vinylidene fluoridee) (PVDF).
View Article and Find Full Text PDFBiosci Biotechnol Biochem
December 2024
Department of Agricultural Chemistry, Graduate School of Agricultural Science, Tohoku University, Sendai, Miyagi, Japan.
Escherichia coli expressing SrPlsAR from Selenomonas ruminantium produces plasmalogen, comprising almost 60% of the total phospholipid content under anaerobic conditions. Both plasmenylethanolamine and plasmenylglycerol were detected, and the major acyl aldehyde derived from sn-1 vinyl ether was C16:1. Plasmalogen synthesis is affected by mutations in ATP-binding sites and Cys expected to be involved in the formation of the [4Fe-4S] cluster.
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