434-90-2Relevant articles and documents
Ullmann reaction optimization within bitolyl and decafluorobiphenyl synthesis
Kolotaev,Razinov,Khachatryan
, p. 993 - 999 (2018)
This article describes the investigation of the cross-coupling Ullman's reaction of aryl halides under various conditions to find optimal scalable method of biaryl synthesis and the development of preparative methods of synthesizing 3,3'-bitolyl and perfluorobipfenyl, which are valuable semi-products of organic synthesis.
Selective reductive defluorination of dicyclohexyl compounds: Intramolecular coupling reaction by reductive cleavage of C-F bonds
Sung, Kuangsen,Lagow, Richard J.
, p. 637 - 638 (1998)
Reductive defluorination of perfluoro(dicyclohexyl ether) 1 with benzophenone anion radical in tetrahydrofuran produces perfluoro(dibenzofuran) 2 with a surprising ring-closure, whereas reductive defluorination of perfluoro(dicyclohexyl) 4 under the same conditions gives perfluoro(diphenyl) 6 with no products involving ring-closure.
Convenient Synthesis of Symmetrical Polyfluorinated Diphenyl Sulfides
Bredikhin, R. A.,Maksimov, A. M.,Nikul’shin, P. V.,Platonov, V. E.
, p. 1921 - 1930 (2022/01/24)
Abstract: Thermal properties of decafluorodiphenyl disulfide in the pure state and in the presence of copper and iron metals have been studied. A procedure has been proposed for the synthesis of symmetrical poly-fluorinated diaryl sulfides from diaryl dis
Palladium-Catalyzed Homocoupling of Highly Fluorinated Arylboronates: Studies of the Influence of Strongly vs Weakly Coordinating Solvents on the Reductive Elimination Process
Budiman, Yudha P.,Friedrich, Alexandra,Jayaraman, Arumugam,Kerner, Florian,Marder, Todd B.,Radius, Udo
supporting information, p. 6036 - 6050 (2020/04/27)
C-C reductive elimination from [PdL2(C6F5)2] to form polyfluorinated biaryls has been a challenge for over 50 years. Thus, palladium-catalyzed homocoupling of arylboronates (ArF-Bpin) containing two ortho-fluorine substituents is very difficult, as the reaction typically stops at the [PdL2(ArF)2] stage after two transmetalation steps. The transmetalated complexes cis-[Pd(MeCN)2(C6F5)2] (3a), cis-[Pd(MeCN)2(2,4,6-C6F3H2)2] (3b), and cis-[Pd(MeCN)2(2,6-C6F2H3)2] (3e) have been isolated from the reaction of ArF-Bpin with Pd(OAc)2 in acetonitrile solvent, with no homocoupling observed. However, catalytic homocoupling proceeds smoothly in a "weakly coordinating" arene solvent as long as no ancillary ligands or coordinating solvents are present. DFT computations reveal that the active catalyst formed by arene solvent coordination leads to an overall reduced barrier for the reductive elimination step compared to the formation of stable [PdL2(ArF)2] complexes in the presence of a donor ligand or solvent L.
Ranking Ligands by Their Ability to Ease (C6F5)2NiIIL → Ni0L + (C6F5)2Coupling versus Hydrolysis: Outstanding Activity of PEWO Ligands
Ponce-De-León, Jaime,Gioria, Estefania,Martínez-Ilarduya, Jesús M.,Espinet, Pablo
supporting information, p. 18287 - 18294 (2020/12/23)
The NiII literature complex cis-[Ni(C6F5)2(THF)2] is a synthon of cis-Ni(C6F5)2 that allows us to establish a protocol to measure and compare the ligand effect on the NiII → Ni0 reductive elimination step (coupling), often critical in catalytic processes. Several ligands of different types were submitted to this Ni-meter comparison: Bipyridines, chelating diphosphines, monodentate phosphines, PR2(biaryl) phosphines, and PEWO ligands (phosphines with one potentially chelate electron-withdrawing olefin). Extremely different C6F5-C6F5 coupling rates, ranging from totally inactive (producing stable complexes at room temperature) to those inducing almost instantaneous coupling at 25 °C, were found for the different ligands tested. The PR2(biaryl) ligands, very efficient for coupling in Pd, are slow and inefficient in Ni, and the reason for this difference is examined. In contrast, PEWO type ligands are amazingly efficient and provide the lowest coupling barriers ever observed for NiII complexes; they yield up to 96% C6F5-C6F5 coupling in 5 min at 25 °C (the rest is C6F5H) and 100% coupling with no hydrolysis in 8 h at-22 to-53 °C.