Redox potentials of trifluoromethyl-containing compounds

Jiang, Yuan‐Ye; Yu, Haizhu; Fu, Yao; Liu, Lei

doi:10.1007/s11426-014-5178-8

Cited by 38 publications

(12 citation statements)

References 44 publications

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“…In the benchmark calculations, the composite high-level ab initio methods, including Gaussian-n (Gn) series (G3, G3B3, , G4, and G4MP2) and complete-basis-set (CBS) series (CBS-QB3, , ROCBS-QB3, CBS-Q, and CBS-APNO , ), which are suitable for systems of less than eight non-hydrogen atoms as well as the 25 kinds of DFT methods including B3LYP, B3LYP-D3, CAM-B3LYP, BP86, B3P86, B3PW91, B97D, B97D3, M05-2X, M06-2X, M06-HF, MPW1B95, MPW1KCIS, TPSS1KCIS, TPSSLYP1W, M11, N12, MN12-L, MN12-SX, PBE1W, PBE1PBE, SOGGA11, SOGGA11-X, WB97, and WB97-X were selected. For all of the DFT calculations, the geometry optimization and the frequency calculation of molecules and the corresponding radicals were conducted at the B3LYP/6-31+G(d) level due to its high accuracy and lower computational cost; − at the same time the correct nature of the stationary points was confirmed and the zero-point vibrational energies (ZPEs) were extracted. The basis set of single-point energy calculation by 25 DFT methods is 6-311++G(2df,2p).…”

Section: Methodsmentioning

confidence: 99%

Computational Study on N–N Homolytic Bond Dissociation Enthalpies of Hydrazine Derivatives

Zheng

Wang

et al. 2018

J. Phys. Chem. A

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The hydrazine derivatives have been regarded as the important building blocks in organic chemistry for the synthesis of organic N-containing compounds. It is important to understand the structure-activity relationship of the thermodynamics of N-N bonds, in particular, their strength as measured by using the homolytic bond dissociation enthalpies (BDEs). We calculated the N-N BDEs of 13 organonitrogen compounds by eight composite high-level ab initio methods including G3, G3B3, G4, G4MP2, CBS-QB3, ROCBS-QB3, CBS-Q, and CBS-APNO. Then 25 density functional theory (DFT) methods were selected for calculating the N-N BDEs of 58 organonitrogen compounds. The M05-2X method can provide the most accurate results with the smallest root-mean-square error (RMSE) of 8.9 kJ/mol. Subsequently, the N-N BDE predictions of different hydrazine derivatives including cycloalkylhydrazines, N-heterocyclic hydrazines, arylhydrazines, and hydrazides as well as the substituent effects were investigated in detail by using the M05-2X method. In addition, the analysis including the natural bond orbital (NBO) as well as the energies of frontier orbitals were performed in order to further understand the essence of the N-N BDE change patterns.

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Section: Methodsmentioning

confidence: 99%

Computational Study on N–N Homolytic Bond Dissociation Enthalpies of Hydrazine Derivatives

Zheng

Wang

et al. 2018

J. Phys. Chem. A

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“…Various putative ·CF 3 sources 35 were tested using model amino acid substrates. Langlois’ reagent (NaTFMS) proved most promising via multiple redox initiation modes (e.g., transition-metal-free, photocatalytic) under mild conditions.…”

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confidence: 99%

Selective Radical Trifluoromethylation of Native Residues in Proteins

et al. 2018

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The incorporation of fluorine can not only significantly facilitate the study of proteins but also potentially modulate their function. Though some biosynthetic methods allow global residue-replacement, post-translational fluorine incorporation would constitute a fast and efficient alternative. Here, we reveal a mild method for direct protein radical trifluoromethylation at native residues as a strategy for symmetric-multifluorine incorporation on mg scales with high recoveries. High selectivity toward tryptophan residues enhanced the utility of this direct trifluoromethylation technique allowing ready study of fluorinated protein constructs using 19F-NMR.

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“…It is therefore reasonable to assume that the active species responsible for the FAT to alkyl radicals is [Cu 2 ( L3 ) 2 F 2 ] 2+ . Such a process (shown in eq ) was then computed by density functional calculations at the B3LYP/6-311+G(d)//B3LYP/6-31G(d) level (with IEFPCM model and MeCN solvent), which has been demonstrated to be a fairly accurate tool in dealing with fluoro-containing models. , To reduce the complexity, 2,2′-bipyridine was used in place of L3 in the calculations (eq ), and tert -butyl and isopropyl radicals were used as the models of tertiary and secondary alkyl radicals, respectively. For the reaction of the tert -butyl radical with [Cu 2 (bpy) 2 F 2 ] 2+ in MeCN solution, an activation free energy of 13.3 kcal/mol is computed, and the whole process (from E to F with R = t -Bu) is exothermic by 7.9 kcal/mol.…”

Section: Results and Discussionmentioning

confidence: 99%

Radical Carbofluorination of Unactivated Alkenes with Fluoride Ions

et al. 2018

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The copper-assisted radical carbofluorination of unactivated alkenes with fluoride ions is described. With [Cu(L3)F]HO (L3 = 4,4'-di(methoxycarbonyl)-2,2'-bipyridine) as the fluorine source and [Ag(DMPhen)(MeCN)]BF (DMPhen = 2,9-dimethyl-1,10-phenanthroline) as the chloride scavenger, the reaction of unactivated alkenes with CCl in acetonitrile provided the corresponding carbofluorination products in satisfactory yields. The protocol exhibited a wide functional group compatibility and broad substrate scope and could be extended to the use of a variety of activated alkyl chlorides other than CCl. A copper-catalyzed fluorotrifluoromethylation of unactivated alkenes was then successfully developed with CsF as the fluorine source and Umemoto's reagent as the trifluoromethylating agent. A mechanism involving the fluorine atom transfer from Cu(II)-F complexes to alkyl radicals is proposed.

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Redox potentials of trifluoromethyl-containing compounds

Cited by 38 publications

References 44 publications

Computational Study on N–N Homolytic Bond Dissociation Enthalpies of Hydrazine Derivatives

Computational Study on N–N Homolytic Bond Dissociation Enthalpies of Hydrazine Derivatives

Selective Radical Trifluoromethylation of Native Residues in Proteins

Radical Carbofluorination of Unactivated Alkenes with Fluoride Ions

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