Copper salt-catalysed reaction of perfluoroalkyl halides with olefins

Igumnov, S. M.; Don, Veronika; Vyazkov, V. A.; Narinyan, Karen E.

doi:10.1070/mc2006v016n03abeh002344

Cited by 6 publications

(5 citation statements)

References 13 publications

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“…The complexes [M(η 5 -Cp*)(η 2 -C 2 H 4 ) 2 ] (M = Rh, Ir) are able to initiate the addition of I-i-C 3 F 7 to ethene (entries 1−4) in the absence of any additive, although addition of a base (NaOAc) modestly increases the Radical addition of iodoperfluorolkanes to alkenes initiated by metal salts or complexes has been reported. 10,13,17,34 In this reaction, the main role of the metal species is to transfer one electron to IR F , to give I − and a perfluoroalkyl radical, which reacts with the alkene, initiating a radical chain reacion. To test if the investigated reactions follow a radical mechanism, we carried out the reaction of I-i-C 3 F 7 , ethene, and [Rh(η 5 -Cp*)(η 2 -C 2 H 4 ) 2 ] in the presence of TEMPO ([TEMPO]:[Rh] = 2 equiv).…”

Section: ■ Introductionmentioning

confidence: 57%

Perfluoroalkylation of Coordinated Ethene in Rh(I) and Ir(I) Complexes. Catalytic Addition of Iodoperfluoroalkanes to Ethene

et al. 2017

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The complexes [M(η5-Cp*)(η2-C2H4)2] (M = Rh, Ir) react with iodoperfluoroalkanes to give [M(η5-Cp*)(CH2CH2RF)(μ-I)]2 (main product) and [M(η5-Cp*)(CH2CH2RF)(μ-I)2M(η5-Cp*)I] (RF = t-C4F9, M = Ir; RF = c-C6F11, M = Ir, Rh). Similarly, the complexes [M(η5-Cp*)(η2-C2H4)(PPh3)] react with iodoperfluoroalkanes to give [M(η5-Cp*)(CH2CH2RF)I(PPh3)] (M = Ir, RF = t-C4F9, i-C3F7; M = Rh, RF = t-C4F9). Evidence for the generation of the heptafluoroisopropyl carbanion in the reaction of [Ir(η5-Cp*)(η2-C2H4)(PPh3)] with I-i-C3F7 was obtained, which suggests that the reaction is initiated by the transfer of two electrons from the Ir(I) complex to the iodoperfluoroalkane. The iodo-bridged complexes react with PPh3 to give [M(η5-Cp*)(CH2CH2RF)I(PPh3)] (M = Ir, RF = t-C4F9, c-C6F11; M = Rh, RF = c-C6F11). The complexes [Ir(η5-Cp*)(CH2CH2RF)I(PPh3)] (RF = c-C6F11, i-C3F7) react with AgOTf to give [Ir(η5-Cp*)H(η2-CH2CHRF)(PPh3)]OTf. The analogous reaction of [Ir(η5-Cp*)(CH2CH2-t-C4F9)I(PPh3)] gives CH3CH2-t-C4F9 and [Ir(η5-Cp*)(η2-o-C6H4PPh2)]OTf, which reacts with PPh3 to give [Ir(η5-Cp*)(η2-o-C6H4PPh2)(PPh3)]OTf. This cyclometalated complex and its analogue [Ir(η5-Cp*)(η2-o-C6H4PPh2)(P(p-Tol)3)]OTf are also prepared by the reaction of [Ir(η5-Cp*)(Me)Cl(PPh3)] with AgOTf and PPh3 or P(p-Tol)3. The derivatives [Ir(η5-Cp*)(CH2CH2RF)(PPh3)L]OTf (L = CO, RF = c-C6F11, i-C3F7; L = PPh3, RF = i-C3F7) are isolated in the reactions of the Ir hydrido alkene complexes with CO or PPh3. The reactions of [Rh(η5-Cp*)(CH2CH2RF)I(PR3)] (R = Me, RF = i-C3F7, n-C4F9, t-C4F9; R = Ph, RF = i-C3F7, t-C4F9, c-C6F11) with AgOTf afford unstable triflato complexes that decompose to give CH2CHRF, but in the presence of PR3 the complexes [Rh(η5-Cp*)(CH2CH2RF)(PR3)2]OTf (R = Ph, RF = i-C3F7, t-C4F9, c-C6F11; R = Me, RF = i-C3F7, t-C4F9) were formed. When R = Ph, these complexes are unstable and decompose quantitatively to give [Rh(η5-Cp*)H(PPh3)2]OTf and CH2CHRF. Complexes of the type [M(η5-Cp*)(η2-C2H4)2] (M = Rh, Ir) and [Rh(η5-Cp*)(CH2CH2RF)I(L)] are initiators for the radical addition of IRF to ethene.

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Section: ■ Introductionmentioning

confidence: 57%

Perfluoroalkylation of Coordinated Ethene in Rh(I) and Ir(I) Complexes. Catalytic Addition of Iodoperfluoroalkanes to Ethene

et al. 2017

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“…Another very effective copper-based catalytic system is the Cu(II) acetate–hydrazine hydrate redox system, which allows the preparation of polyfluoroalkyl-substituted derivatives 25 in good to high yields (Scheme ) …”

Section: Chemical Properties Of Polyfluorinated Ethanesmentioning

confidence: 99%

“…Another very effective copper-based catalytic system is the Cu(II) acetate−hydrazine hydrate redox system, which allows the preparation of polyfluoroalkyl-substituted derivatives 25 in good to high yields (Scheme 27). 88 Metallic copper was also used as a catalyst. The postulated 89 mechanism includes the formation of perfluoroethylcopper, the decay of which results in formation of copper and C 2 F 5 -radical.…”

Section: Reactions Involving Free Radicalsmentioning

confidence: 99%

Polyfluorinated Ethanes as Versatile Fluorinated C2-Building Blocks for Organic Synthesis

2015

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“…A single example of the reductive addition to ethylene was also described using hydrazine as a reductant. 12 However, photo-catalytic reactions of Halon 2402 with alkenes have not been described despite the fact that visible light-mediated processes offer mild and convenient protocols for performing radical reactions. 13 Herein, we report that Halon 2402 as well as other fluorinated bromides may add to alkenes using ascorbic acid as a reductant.…”

mentioning

confidence: 99%

“…It was used in ATRA using dithionite or Cp 2 TiCl 2 /Fe as a promoter. A single example of the reductive addition to ethylene was also described using hydrazine as a reductant . However, photocatalytic reactions of Halon 2402 with alkenes have not been described despite the fact that visible light-mediated processes offer mild and convenient protocols for performing radical reactions .…”

mentioning

confidence: 99%