827-15-6Relevant articles and documents
One-pot route to X-perfluoroarenes (X = Br, I) based on FeIII-assisted C-F functionalization and utilization of these arenes as building blocks for crystal engineering involving halogen bonding
Baykov, Sergey V.,Eliseeva, Anastasiya A.,Frontera, Antonio,Galmés, Bartomeu,Kukushkin, Vadim Yu.,Rozhkov, Anton V.
, p. 5908 - 5921 (2020/10/13)
Perfluorinated arenes (benzeneF derivatives, diphenylF, naphthaleneF) were converted into X-perfluoroarenes (X = Br, I) via the developed one-pot protocol based on [Fe(acetylacetonate)3]-assisted C-F functionalization. The syntheses proceed under mild conditions and employ readily available perfluorinated arenes, which are treated with EtMgBr followed by addition of X2/[Fe(acetylacetonate)3] (0.8 mol %); yields range from good to moderate. The σ-hole donor properties of the obtained mono- and di-X-perfluoroarenes and the significance of these species for halogen-bonding-based crystal engineering was illustrated in a series of postsynthetic experiments, all supported by density functional theory (DFT) energy calculations, molecular electrostatic potential (MEP) surface analysis, and the quantum theory of atoms in molecules (QTAIM). These include (i) a solid-state X-ray diffraction study of X-perfluoroarene self-association (dimerization) via iodine σ-hole - electron belt interactions (three X-ray structures) and (ii) verification of X-perfluoroarene σ-hole donor abilities by their interactions with iodides acting as external σ-hole acceptors (five X-ray structures); a Hirshfeld surface analysis was performed for all eight structures.
Decarboxylative Suzuki-Miyaura coupling of (hetero)aromatic carboxylic acids using iodine as the terminal oxidant
Quibell, Jacob M.,Duan, Guojian,Perry, Gregory J.P.,Larrosa, Igor
supporting information, p. 6445 - 6448 (2019/06/07)
A novel methodology for the decarboxylative Suzuki-Miyaura-type coupling has been established. This process uses iodine or a bromine source as both the decarboxylation mediator and the terminal oxidant, thus avoiding the need for stoichiometric amounts of transition metal salts previously required. Our new protocol allows for the construction of valuable biaryl architectures through the coupling of (hetero)aromatic carboxylic acids with arylboronic acids. The scope of this decarboxylative Suzuki reaction has been greatly diversified, allowing for previously inaccessible non-ortho-substituted aromatic acids to undergo this transformation. The procedure also benefits from low catalyst loadings and the absence of stoichiometric transition metal additives.
T -BuONa-mediated direct C-H halogenation of electron-deficient (hetero)arenes
Liu, Xia,Zhao, Xin,Liang, Fushun,Ren, Baoyi
supporting information, p. 886 - 890 (2018/02/19)
An efficient halogenation of electron-deficient (hetero)arenes is described. The reaction utilizes common t-BuONa as a catalyst (for iodination) or a promoter (for bromination and chlorination), and perfluorobutyl iodide, CBr4 or CCl4 as the readily-available halogenating agents, respectively. The protocol features broad scope, high efficiency, mild conditions and gram scalability. An ionic pathway involving halogen bond formation and halophilic attack is proposed. The utility of the resulting iodinated heteroarenes is demonstrated in visible light-mediated Caryl-Caryl cross-coupling reaction.
Utilising Sodium-Mediated Ferration for Regioselective Functionalisation of Fluoroarenes via C?H and C?F Bond Activations
Maddock, Lewis C. H.,Nixon, Tracy,Kennedy, Alan R.,Probert, Michael R.,Clegg, William,Hevia, Eva
supporting information, p. 187 - 191 (2017/12/07)
Pairing iron bis(amide) Fe(HMDS)2 with Na(HMDS) to form new sodium ferrate base [(dioxane)0.5?NaFe(HMDS)3] (1) enables regioselective mono and di-ferration (via direct Fe?H exchange) of a wide range of fluoroaromatic substrates under mild reaction conditions. Trapping of several ferrated intermediates has provided key insight into how synchronised Na/Fe cooperation operates in these transformations. Furthermore, using excess 1 at 80 °C switches on a remarkable cascade process inducing the collective twofold C?H/threefold C?F bond activations, where each C?H bond is transformed to a C?Fe bond whereas each C?F bond is transformed into a C?N bond.
Unexpected reactivity of cyclic perfluorinated iodanes with electrophiles
Gruber, Stefan,Ametamey, Simon M.,Schibli, Roger
supporting information, p. 8999 - 9002 (2018/08/21)
We have found that cyclic perfluorinated iodanes react with electrophiles (E+ = Br, Cl, F, I) to afford perfluorinated E-RF compounds. This reactivity is unexpected since cyclic perfluorinated iodanes are considered as electrophilic reagents that normally react with nucleophiles (e.g. Nu- = SR, OR) to afford Nu-RF products. The utility of this new transformation is demonstrated for a [18F]CF3CF2-containing compound which was prepared from [18F]XeF2 obtained from cyclotron produced [18F]fluoride.
Unexpected distinction in reactivity of pentafluorobenzenesulfonyl halides toward organolithiums and organomagnesium halides
Bardin, Vadim V.,Maksimov, Alexander M.
, p. 731 - 737 (2017/10/16)
C6F5SO2Cl reacts with organolithiums and organomagnesium halides RM (R = Me, Bu, Ph; M = Li, MgX) to give mainly C6F5H and C6F5Cl. C6F5SO2Br and
Transition-Metal-Free Decarboxylative Iodination: New Routes for Decarboxylative Oxidative Cross-Couplings
Perry, Gregory J. P.,Quibell, Jacob M.,Panigrahi, Adyasha,Larrosa, Igor
supporting information, p. 11527 - 11536 (2017/08/30)
Constructing products of high synthetic value from inexpensive and abundant starting materials is of great importance. Aryl iodides are essential building blocks for the synthesis of functional molecules, and efficient methods for their synthesis from chemical feedstocks are highly sought after. Here we report a low-cost decarboxylative iodination that occurs simply from readily available benzoic acids and I2. The reaction is scalable and the scope and robustness of the reaction is thoroughly examined. Mechanistic studies suggest that this reaction does not proceed via a radical mechanism, which is in contrast to classical Hunsdiecker-type decarboxylative halogenations. In addition, DFT studies allow comparisons to be made between our procedure and current transition-metal-catalyzed decarboxylations. The utility of this procedure is demonstrated in its application to oxidative cross-couplings of aromatics via decarboxylative/C-H or double decarboxylative activations that use I2 as the terminal oxidant. This strategy allows the preparation of biaryls previously inaccessible via decarboxylative methods and holds other advantages over existing decarboxylative oxidative couplings, as stoichiometric transition metals are avoided.
Method for preparing halogenated (hetero) aromatic hydrocarbons
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Paragraph 0041; 0042, (2018/03/24)
The invention relates to a method for preparing halogenated (hetero) aromatic hydrocarbons. The halogenated (hetero) aromatic hydrocarbons are prepared from cheap and easily available perfluorobutyl iodide, carbon tetrabromide and carbon tetrachloride as iodinated, brominated and chlorinated reagents respectively under the action of alkali catalysis (promotion). The method comprises the following steps: firstly, (hetero) aromatic hydrocarbons, a halogenated reagent and an inorganic base are placed in an organic solvent, stirred at room temperature and monitored with TLC until a substrate disappears, and the reaction is stopped; then, a reaction mixed solution is poured into water and extracted, an organic phase is dried, and the organic solvent is removed under reduced pressure; finally, silica-gel column chromatography is performed on a crude product, and a product is obtained. Purification can also be performed by recrystallization. The method has the advantages that the synthetic route is wide in substrate range, raw materials and reagents are cheap and easily available, operation is simple, conditions are mild, yield is high, energy consumption is reduced, the reaction route is safe, gram-grade preparation can be performed and the like.
Preparation method of pentafluoroiodobenzene
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Paragraph 0022; 0023; 0024; 0025; 0026; 0027, (2017/02/24)
The invention relates to a preparation method of pentafluoroiodobenzene and belongs to the technical field of chemical industry, particularly to the field of chemical synthesis. The preparation method enables pentafluorobenzene and iodosuccinimide to react in concentrated sulfuric acid, wherein a molar ratio of the pentafluorobenzene, the iodosuccinimide and the concentrated sulfuric acid is 1:(1-1.5):(5-7.5). The pentafluoroiodobenzene prepared by using the method provided herein has high purity and yield, and the method produces little three wastes, is simple to performance and is easy to industrialize.
Selective CH Functionalization of Methane, Ethane, and Propane by a Perfluoroarene Iodine(III) Complex
Konnick, Michael M.,Hashiguchi, Brian G.,Devarajan, Deepa,Boaz, Nicholas C.,Gunnoe, T. Brent,Groves, John T.,Gunsalus, Niles,Ess, Daniel H.,Periana, Roy A.
supporting information, p. 10490 - 10494 (2016/02/18)
Direct partial oxidation of methane, ethane, and propane to their respective trifluoroacetate esters is achieved by a homogeneous hypervalent iodine(III) complex in non-superacidic (trifluoroacetic acid) solvent. The reaction is highly selective for ester formation (>99 %). In the case of ethane, greater than 0.5 M EtTFA can be achieved. Preliminary kinetic analysis and density functional calculations support a nonradical electrophilic CH activation and iodine alkyl functionalization mechanism. Gas up: Direct partial oxidation of methane, ethane, and propane to their respective trifluoroacetate (TFA) esters is achieved by a homogeneous hypervalent iodine(III) complex in non-superacidic solvent (HTFA). The reaction is highly selective, and for ethane, greater than 0.5 M Et=TFA can be achieved. Preliminary kinetic analysis and density functional calculations support a nonradical electrophilic CH activation and iodine alkyl functionalization mechanism.
