C–H and C–F bond activation reactions of pentafluorostyrene at rhodium complexes

Xu, Conghui; Talavera, María; Sander, Stefan; Braun, Thomas

doi:10.1039/c9dt03371h

Cited by 6 publications

(15 citation statements)

References 86 publications

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“…Thus, the Markovnikov product C 6 F 5 CH(Bpin)CH 3 was afforded under mild conditions with more than 80% selectivity. 52 In contrast, previous studies with rhodium catalysts afforded low selectivity when using pinacolborane as the hydrogen source. 60 However, hydroboration reactions with high selectivities have also been achieved using catecholborane.…”

Section: Account Synlettmentioning

confidence: 86%

“…Treatment of pentafluorostyrene with [Rh(H)(PEt 3 ) 3 ] (1) led initially to coordination of the olefin at the rhodium center to give [Rh(H)(η 2 -CH 2 CHC 6 F 5 )(PEt 3 ) 3 ] (38) (Scheme 16). 52 As discussed for other olefins, insertion of the olefin into the Rh-H bond then occurred. However, instead of -hydride elimination which would lead to the starting materials, the reaction underwent an intramolecular C-F bond oxidative addition at the rhodium center resulting in the rhodaindane fluorido complex trans-[Rh(F){CH 2 CH 2 (2-C 6 F 4 )}(PEt 3 ) 2 ] (39).…”

Section: Account Synlettmentioning

confidence: 87%

“…58 The complex trans-[Rh(F){CH 2 CH 2 (2-C 6 F 4 )}(PEt 3 ) 2 ] (39) is, in the presence of phosphine, in equilibrium with [Rh(F){CH 2 CH 2 (2-C 6 F 4 )}(PEt 3 ) 3 ] (47) (see Scheme 16). 52 The structure of the latter complex was determined by X-ray crystallography. Both complexes revealed instability on a longer time scale or in the presence of KPF 6 .…”

Section: Reactivity Of 333-trifluoropropenementioning

confidence: 99%

“…Otherwise the alkene complex 38 and [Rh(H)(η 2 -CH(Bpin)CHC 6 F 5 )(PEt 3 ) 3 ] (50) are furnished. 52 For comparison, styrene also reacts with [Rh(Bpin)(PEt 3 ) 3 ] (3) to yield the dehydrogenative borylation product (E)-PhCH=CHBpin and the rhodium hydrido complex 1. 59…”

Section: Reactivity Of 333-trifluoropropenementioning

confidence: 99%

“…The C-H bond activation occurred selectively and [Rh{(E)-CH=CHC 6 F 4 }(PEt 3 ) 3 ] (51) was isolated (Scheme 18). 52 This reaction route broadens the scope for C-H bond activation as it allows for cleavage of olefinic C-H bonds in the presence of C-F bonds.…”

Section: Scheme 18 Reactivity Of Complexes 3 and 31 With Pentafluorosmentioning

confidence: 99%

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Rhodium(I) Complexes as Useful Tools for the Activation of Fluoroolefins

Talavera

Braun²

2020

Synlett

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In this account we describe studies on the reactivity of rhodium(I) complexes of the type [Rh(E)(PEt3)3], where E represents hydrido, fluorido, germyl, boryl or silyl ligands, towards fluorinated olefins. The results are compared with those reported by other research groups on fluoroolefins, as well as with the chemistry of compounds [Rh(E)(PEt3)3] towards fluoroaromatics in terms of selectivity and mechanisms.1 Introduction2 Reactivity Towards Fluoroolefins2.1 Reactivity of Hexafluoropropene2.2 Reactivity of (E)-1,2,3,3,3-Pentafluoropropene2.3 Reactivity of 2,3,3,3-Tetrafluoropropene and (E)-1,3,3,3-Tetrafluoropropene2.4 Reactivity of 3,3,3-Trifluoropropene2.5 Reactivity of Pentafluorostyrene3 Conclusion and Perspective

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Section: Account Synlettmentioning

confidence: 86%

Section: Account Synlettmentioning

confidence: 87%

Section: Reactivity Of 333-trifluoropropenementioning

confidence: 99%

Section: Reactivity Of 333-trifluoropropenementioning

confidence: 99%

Section: Scheme 18 Reactivity Of Complexes 3 and 31 With Pentafluorosmentioning

confidence: 99%

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Rhodium(I) Complexes as Useful Tools for the Activation of Fluoroolefins

Talavera

Braun²

2020

Synlett

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Versatile Reaction Pathways of 1,1,3,3,3‐Pentafluoropropene at Rh(I) Complexes [Rh(E)(PEt₃)₃] (E=H, GePh₃, Si(OEt)₃, F, Cl): C‐F versus C‐H Bond Activation Steps

Talavera

Braun

2021

Chemistry A European J

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The reaction of the rhodium(I) complexes [Rh(E)(PEt3)3] (E=GePh3 (1), H (6), F (7)) with 1,1,3,3,3‐pentafluoropropene afforded the defluorinative germylation products Z/E‐2‐(triphenylgermyl)‐1,3,3,3‐tetrafluoropropene and the fluorido complex [Rh(F)(CF3CHCF2)(PEt3)2] (2) together with the fluorophosphorane E‐(CF3)CH=CF(PFEt3). For [Rh(Si(OEt)3)(PEt3)3] (4) the coordination of the fluoroolefin was found to give [Rh{Si(OEt)3}(CF3CHCF2)(PEt3)2] (5). Two equivalents of complex 2 reacted further by C−F bond oxidative addition to yield [Rh(CF=CHCF3)(PEt3)2(μ‐F)3Rh(CF3CHCF2)(PEt3)] (9). The role of the fluorido ligand on the reactivity of complex 2 was assessed by comparison with the analogous chlorido complex. The use of complexes 1, 4 and 6 as catalysts for the derivatization of 1,1,3,3,3‐pentafluoropropene provided products, which were generated by hydrodefluorination, hydrometallation and germylation reactions.

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Synthesis of Alkylated Polyfluorobenzenes through Decarboxylative Giese Addition of Aliphatic N-Hydroxyphthalimide Esters with Polyfluorostyrene

Zeng,

Qu,

Tao

et al. 2023

J. Org. Chem.

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Polyfluoroaromatic compounds play crucial roles in medicinal and material science. However, the synthesis of alkylated polyfluoroarenes has been relatively underdeveloped. In this study, we devised a novel decarboxylative coupling reaction between aliphatic N-hydroxyphthalimide esters and polyfluorostyrene, leveraging the photochemical activity of electron donor− acceptor (EDA) complexes. This method offers simple reaction conditions, a broad substrate scope, and excellent functional group tolerance. Furthermore, we have demonstrated the practicality of this protocol through late-stage polyfluoroaryl modification of biologically active molecules using readily available carboxylic acids as starting materials, thus providing an important supplement to the current toolbox for accessing alkylated polyfluoroaryl motifs.

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C–H and C–F bond activation reactions of pentafluorostyrene at rhodium complexes

Abstract: Reactions of various Rh(i) complexes towards penta-fluorostyrene or its borylated derivative afforded coordination and C–F bond or C–H bond activation reactions.

Cited by 6 publications

References 86 publications

Rhodium(I) Complexes as Useful Tools for the Activation of Fluoroolefins

Rhodium(I) Complexes as Useful Tools for the Activation of Fluoroolefins

Versatile Reaction Pathways of 1,1,3,3,3‐Pentafluoropropene at Rh(I) Complexes [Rh(E)(PEt₃)₃] (E=H, GePh₃, Si(OEt)₃, F, Cl): C‐F versus C‐H Bond Activation Steps

Synthesis of Alkylated Polyfluorobenzenes through Decarboxylative Giese Addition of Aliphatic N-Hydroxyphthalimide Esters with Polyfluorostyrene

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C–H and C–F bond activation reactions of pentafluorostyrene at rhodium complexes

Abstract: Reactions of various Rh(i) complexes towards penta-fluorostyrene or its borylated derivative afforded coordination and C–F bond or C–H bond activation reactions.

Cited by 6 publications

References 86 publications

Rhodium(I) Complexes as Useful Tools for the Activation of Fluoroolefins

Rhodium(I) Complexes as Useful Tools for the Activation of Fluoroolefins

Versatile Reaction Pathways of 1,1,3,3,3‐Pentafluoropropene at Rh(I) Complexes [Rh(E)(PEt3)3] (E=H, GePh3, Si(OEt)3, F, Cl): C‐F versus C‐H Bond Activation Steps

Synthesis of Alkylated Polyfluorobenzenes through Decarboxylative Giese Addition of Aliphatic N-Hydroxyphthalimide Esters with Polyfluorostyrene

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Versatile Reaction Pathways of 1,1,3,3,3‐Pentafluoropropene at Rh(I) Complexes [Rh(E)(PEt₃)₃] (E=H, GePh₃, Si(OEt)₃, F, Cl): C‐F versus C‐H Bond Activation Steps