392-69-8Relevant academic research and scientific papers
Selective Aryl-Fluoride Reductive Elimination from a Platinum(IV) Complex
Dubinsky-Davidchik, Ina,Goldberg, Israel,Vigalok, Arkadi,Vedernikov, Andrei N.
, p. 12447 - 12451 (2015)
A difluoro(mesityl)platinum(IV) complex underwent highly selective reductive elimination of 2-fluoromesitylene upon heating in toluene. Kinetic analysis and DFT calculations suggest that the C-F coupling involves a five-coordinate PtIV transient intermediate resulting from the rate-limiting dissociation of the pyridine ligand.
Unsymmetrical diaryliodonium phenyltrifluoroborate salts: Synthesis, structure and fluorination
Sadek, Omar,Perrin, David M.,Gras, Emmanuel
, p. 68 - 74 (2019)
The unprecedented reaction of organotrifluoroborates salts of unsymmetrical diaryliodoniums to give aryl fluorides is presented. This preliminary report describes the first synthesis of unsymmetrical diaryliodonium phenyltrifluoroborates along with an exe
Dediazoniation of Arenediazonium Ions. Part XIX. Effect of Thiocyanate Ion in the Reactions of 2,4,6-Trimethylbenzenediazonium Tetrafluoroborate in 2,2,2-trifluoroethanol
Szele, Ivanka,Zollinger, Heinrich,Deshpande, Ashok D.
, p. 2721 - 2727 (1981)
The dediazoniation of 2,4,6-trimethylbenzenediazonium tetrafluoroborate (1) in 2,2,2-trifluoroethanol (TFE) was studied in the presence of potassium thiocyanate.The effect of added salt on the dediazoniation rate, the Nα-Nβ rearrangement (Eqn. 2), the exchange of the 15N-labelled diazo group with molecular nitrogen (Eqn. 3), and the reaction products was determinated.With 0.3M KSCN a dediazoniation-rate increase of 16.5percent was achieved, and the amounts of rearranged and exchanged product were reduced to 88percent and 70percent, respectively, of the values found in pure TFE.The dediazoniation products formed are ArF (3), ArOCH2CF3 (4), ArSCN (5), ArNCS (6) and traces of 5,7-dimethylindazole (7).All the data are in agreement with, and support the previously proposed mechanism (Eqn. 1) of heterolytic dediazoniation of arenediazonium salts.
Strategy for Selective Csp2-F and Csp2-Csp2Formations from Organoplatinum Complexes
Sarkissian, Elin,Golbon Haghighi, Mohsen
supporting information, p. 1016 - 1020 (2021/02/05)
By changing the parameters of fluorination reaction of bisaryl-platinum(II) complexes, each possible competitive pathway of Ar-Ar and Ar-F formation can be selectively controlled. It was discovered that steric hindrance, type of fluorinating reagent, and
Photoredox catalysis with aryl sulfonium salts enables site-selective late-stage fluorination
Li, Jiakun,Chen, Junting,Sang, Ruocheng,Ham, Won-Seok,Plutschack, Matthew B.,Berger, Florian,Chabbra, Sonia,Schnegg, Alexander,Genicot, Christophe,Ritter, Tobias
, p. 56 - 62 (2019/11/28)
Photoredox catalysis, especially in combination with transition metal catalysis, can produce redox states of transition metal catalysts to facilitate challenging bond formations that are not readily accessible in conventional redox catalysis. For arene functionalization, metallophotoredox catalysis has successfully made use of the same leaving groups as those valuable in conventional cross-coupling catalysis, such as bromide. Yet the redox potentials of common photoredox catalysts are not sufficient to reduce most aryl bromides, so synthetically useful aryl radicals are often not directly available. Therefore, the development of a distinct leaving group more appropriately matched in redox potential could enable new reactivity manifolds for metallophotoredox catalysis, especially if arylcopper(iii) complexes are accessible, from which the most challenging bond-forming reactions can occur. Here we show the conceptual advantages of aryl thianthrenium salts for metallophotoredox catalysis, and their utility in site-selective late-stage aromatic fluorination.
Expanding the Balz–Schiemann Reaction: Organotrifluoroborates Serve as Competent Sources of Fluoride Ion for Fluoro-Dediazoniation
Mohy El Dine, Tharwat,Sadek, Omar,Gras, Emmanuel,Perrin, David M.
supporting information, p. 14933 - 14937 (2018/09/25)
The Balz–Schiemann reaction endures as a method for the preparation of (hetero)aryl fluorides yet is eschewed due to the need for harsh conditions or high temperatures along with the need to isolate potentially explosive diazonium salts. In a departure from these conditions, we show that various organotrifluoroborates (RBF3?s) may serve as fluoride ion sources for solution-phase fluoro-dediazoniation in organic solvents under mild conditions. This methodology was successfully extended to a one-pot process obviating aryl diazonium salt isolation. Sterically hindered (hetero)anilines are fluorinated under unprecedentedly mild conditions in good-to-excellent yields. Taken together, this work expands the repertoire of RBF3?s to act as fluorine ion sources in an update to the classic Balz–Schiemann reaction.
Hypervalent Iodine(III)-Catalyzed Balz–Schiemann Fluorination under Mild Conditions
Xing, Bo,Ni, Chuanfa,Hu, Jinbo
, p. 9896 - 9900 (2018/07/31)
An unprecedented hypervalent iodine(III) catalyzed Balz–Schiemann reaction is described. In the presence of a hypervalent iodine compound, the fluorination reaction proceeds under mild conditions (25–60 °C), and features a wide substrate scope and good functional-group compatibility.
Application of trivalent iodine compounds as catalysts in Bal-Schiemann reaction
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Paragraph 0152; 0158, (2018/10/19)
The invention discloses an application of trivalent iodine compounds shown in formula I and/or II in the description and used as catalysts in Bal-Schiemann reaction. The trivalent iodine compounds areused as the catalysts in the Bal-Schiemann reaction, so that the Bal-Schiemann reaction can be conducted at room temperature or near room temperature when a thermochemical method is used, and the reaction has mild reaction conditions, wide substrate use range and short reaction time, and is safe and easy to operate, products are easy to separate, and raw materials are simple and low in toxicity.
Mechanistic investigations of Cu-catalyzed fluorination of diaryliodonium salts: Elaborating the CuI/CuIII manifold in copper catalysis
Ichiishi, Naoko,Canty, Allan J.,Yates, Brian F.,Sanford, Melanie S.
supporting information, p. 5525 - 5534 (2015/02/19)
A combination of experimental and density functional theory (DFT) investigations suggests that the Cu-catalyzed fluorination of unsymmetrical diaryliodonium salts with general structure [Mes(Ar)I]+ in N,N′-dimethylformamide proceeds through a CuI/CuIII catalytic cycle. A low concentration of fluoride relative to combined iodonium reagent plus copper ensures that [Mes(Ar)I]+ is available as the reactive species for oxidative "Ar+" transfer to a CuI center containing one or two fluoride ligands. A series of different possible CuI active catalysts (containing fluoride, triflate, and DMF ligands) have been evaluated computationally, and all show low-energy pathways to fluorinated products. The oxidation of these CuI species by [Mes(Ar)I]+ to form cis-Ar(F)CuIII intermediates is proposed to be rate-limiting in all cases. Ar-F bond-forming reductive elimination from CuIII is computed to be very facile in all of the systems examined. The conclusions of the DFT experiments are supported by several experimental studies, including tests showing that CuI is formed rapidly under the reaction conditions and that the fluoride concentration strongly impacts the reaction yields/selectivities.
Cu-catalyzed fluorination of diaryliodonium salts with KF
Ichiishi, Naoko,Canty, Allan J.,Yates, Brian F.,Sanford, Melanie S.
supporting information, p. 5134 - 5137 (2013/10/22)
A mild Cu-catalyzed nucleophilic fluorination of unsymmetrical diaryliodonium salts with KF is described. This protocol preferentially fluorinates the smaller aromatic ligand on iodine(III). The reaction exhibits a broad substrate scope and proceeds with high chemoselectivity and functional group tolerance. DFT calculations implicate a CuI/CuIII catalytic cycle.
