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
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.
Discovery and mechanistic investigation of Pt-catalyzed oxidative homocoupling of benzene with PhI(OAc)2
Abu-Omar, Mahdi M.,Nabavizadeh, S. Masoud,Niroomand Hosseini, Fatemeh,Park, Chan,Wu, Guang
supporting information, p. 2477 - 2486 (2020/03/05)
We present a Pt-catalyzed direct coupling of benzene to biphenyl. This catalytic reaction employs a cyclometalated platinum(ii) complex [PtMe(bhq)(SMe2)] (bhq = benzo[h]quinolate) with PhI(OAc)2 as an oxidant and does not require an acid, a co-catalyst or a solvent. The reaction kinetics and characterization of potential catalytic species are reported. The reaction is first-order in Pt and second-order in benzene, which implicates the second C-H activation step as rate-determining. A Pt(ii)/Pt(iv) catalytic cycle is suggested. The reaction commences by oxidation of the Pt(ii) complex to give the platinum(iv) species [Pt(bhq)(SMe2)(OAc)2](OAc) followed by C-H activation of benzene to afford the intermediate [PtPh(bhq)(SMe2)(OAc)](OAc) concurrently with the release of HOAc. A second benzene molecule reacts similarly to give the diphenyl intermediate [PtPh2(bhq)(SMe2)](OAc). C-C bond forming reductive elimination ensues to regenerate Pt(ii) and complete the catalytic cycle. The proposed mechanism has been examined by DFT computations, which provide support to experimental findings.