: Organic electronics is a rapidly growing field driven in large part by the synthesis of ∏-conjugated molecules and polymers. Traditional aryl cross-coupling reactions such as the Stille and Suzuki have been used extensively in the synthesis of ∏-conjugated molecules and polymers, but the synthesis of intermediates necessary for traditional cross-couplings can include multiple steps with toxic and hazardous reagents. Direct arylation through C-H bond activation has the potential to reduce the number of steps and hazards while being more atom-economical. Within the Center for Selective C-H Functionalization (CCHF), we have been developing C-H activation methodology for the synthesis of ∏-conjugated materials of interest, including direct arylation of difficult-to-functionalize electron acceptor intermediates and living polymerization of ∏-conjugated polymers through C-H activation.
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http://dx.doi.org/10.3390/molecules23040922 | DOI Listing |
Nat Commun
December 2024
State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao, China.
Catalytic upcycling of polyethylene terephthalate (PET) into high-value oxygenated products is a fascinating process, yet it remains challenging. Here, we present a one-step tandem strategy to realize the thermal catalytic oxidation upcycling of PET to terephthalic acid (TPA) and high-value glycolic acid (GA) instead of ethylene glycol (EG). By using the Au/NiO with rich oxygen vacancies as catalyst, we successfully accelerate the hydrolysis of PET, accompanied by obtaining 99% TPA yield and 87.
View Article and Find Full Text PDFChemistry
December 2024
Université de Liège: Universite de Liege, Laboratory of Organometallic Chemistry and Homogeneous Catalysis, Institut de chimie B6a, Sart-Tilman, 4000, Liege, BELGIUM.
Thirteen imidazolium iodides bearing benzyl, mesityl, or 2,6-diiso-propyl-phenyl substituents on their nitrogen atoms, and C1 to C4 alkyl chains on their C2 carbon atom were readily deuterated with D2O as a cheap and non-toxic deuterium source in the presence of Cs2CO3, a weak, innocuous, inorganic base. The isotopic exchange proceeded quickly and efficiently under mild, aerobic conditions to afford a range of aNHC and NHO precursors regioselectively labeled on their C2α exocyclic position and/or C4=C5 heterocyclic backbone. A "carbene-free" mechanism was postulated, in which the carbonate anion acts as a catalyst to activate an exocyclic, acidic C-H bond and ease a deuterium transfer from D2O to the imidazolium salt in a concerted fashion.
View Article and Find Full Text PDFChemistry
December 2024
Sapienza Università di Roma, Chemistry, Piazzale Aldo Moro 5, Dipartimento di Chimica, edificio CU 014, 00185, Rome, ITALY.
The outstanding efficiency and selectivity of enzymatic reactions, such as C-H oxidation by nonheme iron oxygenases, stems from a precise control of substrate positioning inside the active site. The resulting proximity between a specific moiety (a certain C-H bond) to the reactant (a FeIV(O) active species) translates into higher rates and selectivity, that can be in part replicated also with artificial supramolecular catalysts. However, structural modification of the position and orientation of the binding site both in enzymes and in artificial catalysts often leads to significant variations in reactivity that can be difficult to rationalize due to the system's complexity.
View Article and Find Full Text PDFChem Asian J
December 2024
CSIR-IHBT: Institute of Himalayan Bioresource Technology CSIR, Chemical Technology, Palampur, India, Palampur, 176061, Palampur, INDIA.
Quinolines have emerged as essential components in various medicinal agents, playing a key role in treating various ailments. Numerous drugs with a quinoline core have been recognized for their antimalarial, antibacterial, and anticancer activities and have been successfully commercialized, including chloroquine, ciprofloxacin, topotecan, etc. Over the past two decades, we have witnessed a tremendous expansion in the C-H bond functionalization of quinoline scaffolds to widen this chemical space for drug discovery further.
View Article and Find Full Text PDFJACS Au
December 2024
Department of Chemistry, University of Antwerp, Antwerp 2020, Belgium.
Proton-coupled electron transfer (PCET) is a fundamental redox process and has clear advantages in selectively activating challenging C-H bonds in many biological processes. Intrigued by this activation process, we aimed to develop a facile PCET process in cancer cells by modulating proton tunneling. This approach should lead to the design of an alternative photodynamic therapy (PDT) that depletes the mitochondrial electron transport chain (ETC), the key redox regulator in cancer cells under hypoxia.
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