We report here a photoinduced iron-catalyzed fluoroalkylation-peroxidation of activated and/or unactivated alkenes with fluoroalkyl carboxylic acids and hydroperoxide. The ligand-to-iron charge transfer strategy effectively overcomes the high redox potential of the fluoroalkyl carboxylic acids, facilitating the difunctionalization reaction to occur smoothly under mild reaction conditions. The late-stage functionalization of drug and natural product derivatives was also demonstrated.
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http://dx.doi.org/10.1039/d4cc04650a | DOI Listing |
Chem Commun (Camb)
October 2024
Key Laboratory of Advanced Light Conversion Materials and Biophotonics, School of Chemistry and Life Resources, Renmin University of China, Beijing 100872, China.
We report here a photoinduced iron-catalyzed fluoroalkylation-peroxidation of activated and/or unactivated alkenes with fluoroalkyl carboxylic acids and hydroperoxide. The ligand-to-iron charge transfer strategy effectively overcomes the high redox potential of the fluoroalkyl carboxylic acids, facilitating the difunctionalization reaction to occur smoothly under mild reaction conditions. The late-stage functionalization of drug and natural product derivatives was also demonstrated.
View Article and Find Full Text PDFInorg Chem
May 2022
Department of Chemistry, University of Manitoba, Winnipeg, Manitoba R3T 2N2, Canada.
The position of the experimentally observed (in the UV-vis and magnetic circular dichroism (MCD) spectra) low-energy metal-to-ligand charge-transfer (MLCT) band in low-spin iron(II) phthalocyanine complexes of general formula PcFeL, PcFeL'L″, and [PcFeX] (L, L', or L″ are neutral and X is an anionic axial ligand) was correlated with the Lever's electrochemical scale values for the axial ligands. The time-dependent density functional theory (TDDFT)-predicted UV-vis spectra are in very good agreement with the experimental data for all complexes. In the majority of compounds, TDDFT predicts that the first degenerate MLCT band that correlates with the MCD -term observed between 360 and 480 nm is dominated by an (Fe, d) → (Pc, π*) single-electron excitation (in traditional point group notation) and agrees well with the previous assignment discussed by Stillman and co-workers[ 1994, 33, 573-583].
View Article and Find Full Text PDFInorg Chem
October 2008
Department of Chemistry, Temple Hall 431, Missouri State University, Springfield, Missouri 65897, USA.
Two intensely blue-colored complexes, P(C 6H 5) 4[Fe(BCO) 3] ( 1) and Na[Fe(BCO) 3] ( 2), where BCO (-) is the benzoylcyanoxime anion, have been prepared and characterized in solution and in the solid state. The crystal structure of 1 has been determined at several temperatures (100, 155, 225, and 293 K) and consists of layers of P(C 6H 5) 4 (+) cations and [Fe(BCO) 3] (-) anions. The latter exist as a pair of fac-Delta and Lambda enantiomers in a monoclinic unit cell in the P2(1)/ n space group.
View Article and Find Full Text PDFJ Biol Chem
September 1995
Section of Hematology Research, Mayo Clinic and Foundation, Rochester, Minnesota 55905, USA.
The dsr gene from Desulfovibrio gigas encoding the nonheme iron protein desulforedoxin was cloned using the polymerase chain reaction, expressed in Escherichia coli, and purified to homogeneity. The physical and spectroscopic properties of the recombinant protein resemble those observed for the native protein isolated from D. gigas.
View Article and Find Full Text PDFFree Radic Res
January 1995
L'Oréal Basic Research Center, Aulnay sous bois, France.
During oxidative stress, iron traces are supposed to be released from normal storage sites and to catalyse oxidative damage by Fenton-type reactions. This type of damage is difficult to prevent in vivo except by the use of strong iron chelators such as deferoxamine (affinity constant for Fe(III): log K = 30.8).
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