Palladium mediated activation of a C–F bond in pentafluoropyridine: synthesis, structure and reactivity of a pyridyloxy complex

Braun, Thomas; Rothfeld, Sascha; Schorlemer, Verena; Stammler, Anja; Stammler, Hans‐Georg

doi:10.1016/s1387-7003(03)00099-6

Cited by 33 publications

(16 citation statements)

References 27 publications

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“…242 This can be described as a palladium mediated formal nucleophilic substitution of the fluorine in the para-position although a mechanistic study was not carried out. Similar nucleophilic substitution on the activated para C-F bond of pentafluoropyridine, 243 or on the unactivated site of a monofluoroquinoline have been also reported in stoichiometric processes. 244 [Cat]…”

Section: Scheme 79supporting

confidence: 68%

Palladium-Mediated Organofluorine Chemistry

Albéniz¹,

Casares²

2014

Advances in Organometallic Chemistry

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Section: Scheme 79supporting

confidence: 68%

Palladium-Mediated Organofluorine Chemistry

Albéniz¹,

Casares²

2014

Advances in Organometallic Chemistry

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“…Note that it has been suggested before that [PdMe 2 (Me 2 NCH 2 CH 2 NMe 2 )] ( 4) can induce a substitution of fluorine by a hydroxy group in pentafluoropyridine to give HF and 4-hydroxytetrafluoropyridine from water. 35 We speculate about a similar transformation. Both 25 The existence of square-planar trisphosphine rhodium fluoro complexes also indicates that a phosphine ligand in the trans position to the fluoride might be sufficient.…”

Section: Discussionmentioning

confidence: 79%

“…HF itself could be generated in a palladium-mediated process from pentafluoropyridine in presence of adventitious water, as it has been shown before. 35 Note, that for the synthesis of 1 water has been used in the work-up process. 36 Therefore, we performed the reactions in an NMR tube equipped with a PFA inliner using batches of 1, which had been recrystallised several times.…”

Section: Pentafluoropyridine As Fluoride Sourcementioning

confidence: 99%

Routes to unique palladium A-frame complexes with a bridging fluoro-ligand

et al. 2005

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Treatment of a toluene solution of [PdMe(2)(Cy(2)PCH(2)PCy(2))](1) with pentafluoropyridine in the presence of traces of water affords the generation of the A-frame complexes [(PdMe)(2){mu-kappa(2)(P,P)Cy(2)PCH(2)PCy(2)}(2)(mu-F)][SiMeF(4)]() and [(PdMe)(2){mu-kappa(2)(P,P)Cy(2)PCH(2)PCy(2)}(2)(mu-F)][OC(5)NF(4)](2b). If the reaction is performed in an NMR tube equipped with a PFA inliner, complex 2b is produced, only. Treatment of 1 with pentafluoropyridine in the presence of an excess water yields the pyridyloxy complex [PdMe(OC(5)NF(4))(Cy(2)PCH(2)PCy(2))](3). Compound [(PdMe)(2){mu-kappa(2)(P,P)Cy(2)PCH(2)PCy(2)}(2)(mu-F)][FHF](2c) bearing a bifluoride anion instead of SiMeF(4)(-) or OC(5)NF(4)(-) can be generated by reaction of 1 with substoichiometric amounts of Et(3)N.3HF. The analogous complex [(PdMe)(2){mu-kappa(2)(P,P)Ph(2)PCH(2)PPh(2)}(2)(mu-F)][FHF] (5c) has been synthesized by addition of Ph(2)PCH(2)PPh(2) to a solution of [PdMe(2)(Me(2)NCH(2)CH(2)NMe(2))](4) in THF and subsequent treatment of the reaction mixture with Et(3)N.3HF. The structure of the A-frame complex 5c has been determined by X-ray crystallography.

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“…The heterocycles then might react further without leaving the coordination sphere of the metal. It has been suggested before that the palladium complexes 1 or [PdMe 2 (Me 2 NCH 2 CH 2 NMe 2 )] can induce a substitution of fluorine by a hydroxy group in pentafluoropyridine to give HF and 4-hydroxytetrafluoropyridine from water [6,7]. We speculate about a similar transformation at the palladium center.…”

Section: Resultsmentioning

confidence: 62%

“…Prominent examples are concerned with cross-coupling reactions of fluorinated aromatics [5]. We discovered recently that in a palladium mediated process a carbon-fluorine bond in pentafluoropyridine can be converted into a carbon-oxygen bond yielding pyridyloxy complexes in the presence of water [6,7]. In an alternative reaction pathway the generated HF gives fluoro complexes [7].…”

Section: Introductionmentioning

confidence: 99%