A mild and practical protocol for manganese-catalyzed aerobic oxytrifluoromethylation of olefinic bonds of styrene derivatives using CF3SO2Na (Langlois' reagent) as the CF3 source is described. A distinguishing feature of this method is the generation of trifluoromethyl radicals from CF3SO2Na using the simple manganese salt/O2 system. The reaction proceeds under ambient conditions, free of added peroxide initiators, and provides moderate to good selectivities for alcohol versus ketone product.
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http://dx.doi.org/10.1021/acs.joc.5b00781 | DOI Listing |
J Org Chem
April 2019
Institut Charles Gerhardt Montpellier , Université de Montpellier, UMR 5253 CNRS, ENSCM, 8 rue de l'Ecole Normale , Montpellier 34296 , France.
Ligand-free manganese-catalyzed homocoupling of arenes or aryl halides can be carried out under aerobic conditions via the in situ formation of the corresponding aryllithiums. A wide range of biaryls and derivatives has been obtained, and a mechanism involving monomeric manganese-oxo complexes has been proposed on the basis of DFT calculations.
View Article and Find Full Text PDFChem Pharm Bull (Tokyo)
July 2019
Laboratory of Organic Chemistry for Drug Development and Medicinal Research Laboratories, Graduate School of Pharmaceutical Sciences, Kitasato University.
A novel aerobic manganese-catalyzed oxophosphorylation reaction of carbon-carbon double bonds of styrene derivatives and vinyl ethers using diethyl H-phosphonates was developed. This direct transformation of alkenes to β-ketophosphonate readily proceeded at room temperature via the direct incorporation of molecular oxygen present in air (open flask).
View Article and Find Full Text PDFJ Org Chem
May 2017
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences , Lanzhou 730000, P. R. China.
A novel and efficient synthesis of functionalized oxazoles from 2-amidodihydrofurans has been achieved by alkali-induced intramolecular C-O bond cleavage and formation using air as a green oxidant. Moreover, these functionalized oxazoles could be readily transformed into the corresponding oxazole-substituted pyrazoles and 2H-azirines.
View Article and Find Full Text PDFJ Org Chem
July 2015
‡Department of Chemistry, Lehigh University, 6 East Packer Avenue, Bethlehem, Pennsylvania 18015, United States.
A mild and practical protocol for manganese-catalyzed aerobic oxytrifluoromethylation of olefinic bonds of styrene derivatives using CF3SO2Na (Langlois' reagent) as the CF3 source is described. A distinguishing feature of this method is the generation of trifluoromethyl radicals from CF3SO2Na using the simple manganese salt/O2 system. The reaction proceeds under ambient conditions, free of added peroxide initiators, and provides moderate to good selectivities for alcohol versus ketone product.
View Article and Find Full Text PDFOrg Biomol Chem
July 2013
Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
We describe the first example of manganese(III)-catalyzed aerobic dehydrogenative cyclization producing ring-fused indole skeletons. This catalytic system converts from two C-H bonds of indole and malonate to a C-C bond and produces water as the sole side product. This operationally easy method was extended to an intermolecular cross-dehydrogenative coupling of indole and α-substituted malonate with complete C2-selectivity.
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