Palladium-Catalyzed Cross-Coupling Reactions of Perfluoro Organic Compounds

Ohashi, Masato; Ogoshi, Sensuke

doi:10.3390/catal4030321

Cited by 17 publications

(7 citation statements)

References 112 publications

(110 reference statements)

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“…24 Among reactions of aliphatic hydrofluorocarbons in solution, we draw attention to the reactions of CH 3 F and CHF 3 at iridium pincer complexes 42 and the discovery of niobium complexes that are selective for activation of benzylic CF 3 groups, even in the presence of C-H bonds. 43 Carbon-fluorine bond activation has been the subject of numerous recent reviews, [33][34][44][45][46][47][48][49][50][51][52][53][54][55][56][57][58][59][60][61] but competing C-H bond activation receives little attention in most of these publications. Two reviews pay particular attention to partially fluorinated substrates and C-H activation, one on nickel chemistry 62 and the other on organometallic chemistry particularly with fluorobenzene and difluorobenzene.…”

Section: Scheme 1 Coordination Of Hydrofluoroarenes and Hydrofluoroamentioning

confidence: 99%

“…Carbon–fluorine bond activation has been the subject of numerous recent reviews, ,,− but competing C–H bond activation receives little attention in most of these publications. Two reviews pay particular attention to partially fluorinated substrates and C–H activation, one on nickel chemistry and the other on organometallic chemistry particularly with fluorobenzene and difluorobenzene .…”

Section: Introductionmentioning

confidence: 99%

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Selectivity of C–H Activation and Competition between C–H and C–F Bond Activation at Fluorocarbons

2017

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Partially fluorinated alkanes, arenes, and alkenes can be transformed by a variety of transition metal and lanthanide systems. Although the C-H bond is weaker than the C-F bond regardless of the hybridization of the carbon, the reaction of the C-F bond at the metal is usually more exothermic than the corresponding reaction of the C-H bonds. Both bonds are activated by the metal systems, but the preference for activating these bonds depends on the nature of the hydrocarbon and of the metal system, so that the reaction can be directed exclusively toward C-H or C-F bonds or yield a mixture of products. Additionally, the presence of fluorine differentiates between C-H bonds at different positions resulting in regioselective C-H bond activation; paradoxically, the strongest C-H bond reacts preferentially. The purpose of this review is to describe the field of reactions of partially fluorinated substrates with transition metal atoms, ions, and molecular complexes. The controlling physical properties (thermodynamics and kinetics) are described first, followed by a description of stoichiometric reactions, with the competition between the C-H and C-F activations as focus. A few representative catalytic systems are discussed. The review also highlights the benefit of combining experimental and theoretical studies.

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Section: Scheme 1 Coordination Of Hydrofluoroarenes and Hydrofluoroamentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Selectivity of C–H Activation and Competition between C–H and C–F Bond Activation at Fluorocarbons

2017

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“…Transition-metal complexes having an M–CF 2 – bond are regarded as intermediates in the fluoroalkylation of organic compounds as well as the functionalization and polymerization of fluoroethylenes. − Hughes reported the introduction of fluorinated alkyl ligands into various transition metals, such as Co, Rh, Ir, Mo, and W, via the reactions of R F –I with low-valent metal complexes as well as the chemical properties of the fluoroorganotransition metal complexes . Michelin extensively reviewed recent reports on Pt complexes having fluorinated alkyl ligands and phosphine ligands .…”

Section: Introductionmentioning

confidence: 99%

Fluoroalkylation of a Methylplatinum(II) Complex under Photoirradiation

2017

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The UV irradiation of a mixture of PtMe 2 (cod) (cod = 1,5cyclooctadiene) and n-C 4 F 9 I in a 1:12 molar ratio for 15 min produces Pt(n-C 4 F 9 ) 2 (cod) in 61% yield at room temperature. The reaction without irradiation, as reported previously, proceeds much more slowly; heating the mixture for 7 days at 50 °C forms PtMe(n-C 4 F 9 )(cod) in 9% yield and no Pt(n-C 4 F 9 ) 2 (cod). Pt(n-C 4 F 9 ) 2 (cod) is converted to complexes having chelating ligands, Pt(n-C 4 F 9 ) 2 (L) (L = dppe (1,2-bis(diphenylphosphino)ethane), dppp (1,3-bis(diphenylphosphino)propane), bpy (2,2′-bipyridine)). The photoassisted fluoroalkylation of PtMe(n-C 4 F 9 )(cod) also affords Pt(n-C 4 F 9 ) 2 (cod), while the monomethylplatinum complexes PtMe(C 6 H 4 -4-F)(cod) and PtClMe(cod) react with n-C 4 F 9 I under photoirradiation to afford complexes with a perfluorobutyl ligand, Pt(n-C 4 F 9 )(C 6 H 4 -4-F)(cod) and PtCl(n-C 4 F 9 )(cod), respectively. The above reactions do not provide isolable Pt(IV) complexes, in contrast to the reactions of alkyl or fluoroalkyl iodides with diorganoplatinum(II) complexes having dinitrogen ligands. The mechanism of the fluoroalkylation of Pt(II) complexes under photoirradiation is discussed on the basis of the reaction products.

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“…Among the various approaches, catalytic transformations of organofluoro compounds is one of the most challenging subject. The well-known catalytic transformations, such as hydrodefluorination, 3 Suzuki- Miyaura,4 and Stille 5 C-C cross-coupling, amination reaction, 5 C-F bond activations of multi fluorinated compounds, 6 nucleophilic substitution of electron deficient fluoroarenes 7 and metallofluoroarene complexes, 8 cross-coupling reaction of perfluoro organic compounds, 9 etc. are already well documented in literature.…”

Section: Introductionmentioning

confidence: 99%

Dinuclear Tetrapyrazolyl Palladium Complexes Exhibiting Facile Tandem Transfer Hydrogenation/Suzuki Coupling Reaction of Fluoroarylketone

et al. 2016

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Herein, we report an example of dinuclear pyrazolyl-based Pd complexes exhibiting facile tandem catalysis for fluoroarylketone: Tetrapyrazolyl di-palladium complexes with varying Pd-Pd distances efficiently catalyze the tandem reaction involving transfer hydrogenation of fluoroarylketone to the corresponding alcohol and Suzuki-Miyaura cross coupling reaction of the resulting fluoroarylalcohol under moderate reaction conditions, to biaryl alcohol. The complex with the shortest Pd-Pd distance exhibits the highest tandem activity among its di-metallic analogues, and exceeds in terms of activity and selectivity the analogous mononuclear compound. The kinetics of the reaction indicates clearly that reductive transformation of haloarylketone into haloaryalcohol is the rate determining step in the tandem reaction. Interestingly while fluoroarylketone undergoes the multistep tandem catalysis, the chloro-and bromoarylketones undergo only a single step C-C coupling reaction resulting in biarylketone as the final product. Unlike the pyrazole based Pd compounds, the precursor PdCl 2 and the phosphine based relevant complexes (PPh 3 ) 2 PdCl 2 and (PPh 3 ) 4 Pd are found to be unable to exhibit the tandem catalysis.

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Palladium-Catalyzed Cross-Coupling Reactions of Perfluoro Organic Compounds

Cited by 17 publications

References 112 publications

Selectivity of C–H Activation and Competition between C–H and C–F Bond Activation at Fluorocarbons

Selectivity of C–H Activation and Competition between C–H and C–F Bond Activation at Fluorocarbons

Fluoroalkylation of a Methylplatinum(II) Complex under Photoirradiation

Dinuclear Tetrapyrazolyl Palladium Complexes Exhibiting Facile Tandem Transfer Hydrogenation/Suzuki Coupling Reaction of Fluoroarylketone

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