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We report herein a single component Ir photoredox catalyst which is capable of catalyzing the hydrotrifluoromethylation of terminal alkenes and Michael acceptors with sodium triflinate (Langlois reagent) in methanol under irradiation at room temperature. Various synthetically useful functional groups, including ester, amide, ether, aldehyde, sulfone, ketone and aryl boronate, are well tolerated in this reaction.
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http://dx.doi.org/10.1039/c6cc01944g | DOI Listing |
Chem Sci
February 2024
CAS Key Laboratory of Separation Sciences for Analytical Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences Dalian 116023 China
Due to the complex high-order structures and interactions of proteins within an aqueous solution, a majority of chemical functionalizations happen on the hydrophilic sites of protein external surfaces which are naturally exposed to the solution. However, the hydrophobic pockets inside proteins are crucial for ligand binding and function as catalytic centers and transporting tunnels. Herein, we describe a reagent pre-organization and photochemical trifluoromethylation strategy to profile the functional sites inside the hydrophobic pockets of native proteins.
View Article and Find Full Text PDFJ Org Chem
November 2024
University of Minnesota, Department of Chemistry, Minneapolis, Minnesota 55455, United States.
Sodium triflinate (CFSONa) is an inexpensive bench-stable radical CF source that is often activated by external oxidants such as peroxides. However, despite the commercial accessibility of CFSONa, the salt has never been applied to decarboxylative trifluoromethylation due to challenges in controlled cross-radical coupling. We report a redox-neutral approach to decarboxylative C(sp) trifluoromethylation of carboxylic acid derivatives.
View Article and Find Full Text PDFJ Org Chem
August 2020
Department of Chemistry, Institute of Science, Banaras Hindu University, Varanasi 221005, India.
A metal- and oxidant-free photoinduced strategy for thioxo sulfur-selective trifluoromethylation of β-ketodithioesters at room temperature is reported. Excellent /-stereoselectivity has been achieved with cheap and viable Langlois' reagent (CFSONa, sodium triflinate) in the presence of eosin Y, which acts as a hydrogen atom transfer (HAT) catalyst. The reaction proceeds disulfide intermediate disulfanediylbis(3-(alkylthio)-1-phenylprop-2-en-1-one) (a dimer of β-ketodithioester) followed by complementing proton-coupled electron transfer-mediated reverse HAT cycle of eosin Y.
View Article and Find Full Text PDFJ Am Soc Mass Spectrom
May 2020
Department of Chemistry, Washington University, St. Louis, Missouri 63130, United States.
Synchrotron radiolysis generates hydroxyl radicals (OH) that are successful footprinting reagents. Here, we describe a new reagent for the synchrotron platform, the trifluoromethyl radical (CF). The radical is produced by OH displacement of CF from sodium triflinate (Langlois reagent).
View Article and Find Full Text PDFOrg Biomol Chem
April 2019
Institute of Chemistry, University of Graz, NAWI Graz, Heinrichstrasse 28, 8010, Graz, Austria.
An in-depth study of the reaction of electrochemically generated trifluoromethyl radicals with aryl alkynes in the presence of water is presented. The radicals are readily generated by anodic oxidation of sodium triflinate, an inexpensive and readily available CF3 source, with concomitant reduction of water. Two competitive pathways, i.
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