Pd/Ni-Catalyzed Germa-Suzuki coupling <i>via</i> dual Ge–F bond activation

Kameo, Hajime; Mushiake, Akihiro; Isasa, Tomohito; Matsuzaka, Hiroyuki; Bourissou, Didier

doi:10.1039/d1cc01392k

Cited by 18 publications

(15 citation statements)

References 46 publications

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“…We postulated that coordination of the alkali metal (Li or Na) to the alkyl halide position likely reduces the barrier for S N 2 attack by 1 , in a mechanism reminiscent of FLP activation of alkyl, silyl, and germyl fluorides . A series of kinetic experiments were performed to support our hypothesis.…”

Section: Results and Discussionmentioning

confidence: 87%

Alkali Metal Adducts of an Iron(0) Complex and Their Synergistic FLP-Type Activation of Aliphatic C–X Bonds

et al. 2021

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We report the formation and full characterization of weak adducts between Li+ and Na+ cations and a neutral iron(0) complex, [Fe(CO)3(PMe3)2] (1), supported by weakly coordinating [BArF 20] anions, [1·M][BArF 20] (M = Li, Na). The adducts are found to synergistically activate aliphatic C–X bonds (X = F, Cl, Br, I, OMs, OTf), leading to the formation of iron(II) organyl compounds of the type [FeR(CO)3(PMe3)2][BArF 20], of which several were isolated and fully characterized. Stoichiometric reactions with the resulting iron(II) organyl compounds show that this system can be utilized for homocoupling and cross-coupling reactions and the formation of new C–E bonds (E = C, H, O, N, S). Further, we utilize [1·M][BArF 20] as a catalyst in a simple hydrodehalogenation reaction under mild conditions to showcase its potential use in catalytic reactions. Finally, the mechanism of activation is probed using DFT and kinetic experiments that reveal that the alkali metal and iron(0) center cooperate to cleave C–X via a mechanism closely related to intramolecular FLP activation.

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Section: Results and Discussionmentioning

confidence: 87%

Alkali Metal Adducts of an Iron(0) Complex and Their Synergistic FLP-Type Activation of Aliphatic C–X Bonds

et al. 2021

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“…As an entry point, we targeted complex 1 -Ph (Figure ). Reaction of the known ligand (Ph)(Cl)( o -dppp) 2 Ge ( o -dppp = o -(Ph 2 P)C 6 H 4 ) with [(Ph 3 P) 2 Pt(C 2 H 4 )] proceeds with oxidative addition of the Ge–Cl bond on Pt, affording complex 1 -Ph (Scheme ). This complex, which is reminiscent of the known palladium catalysts of general formula [( o -(R 2 P)C 6 H 4 ) 2 GeMe]PdCl (R = alkyl or aryl group), gives rise to a single peak at 56.2 ppm in the 31 P NMR spectrum, flanked by 195 Pt satellites.…”

Section: Resultsmentioning

confidence: 99%

Photoreductive Elimination of PhCl Across the Dinuclear Core of a [GePt]^VI Complex

Karimi

Gabbaı̈

2022

Organometallics

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As part of our interest in the photochemistry of platinum/p-block element complexes, we now report on the synthesis and photoreduction of [(Ph)((o-Ph 2 P)C 6 H 4 ) 2 GePtCl 3 ] (2-Ph), a complex featuring a tetravalent platinum center connected to a germyl ligand. When in the presence of a chlorine trap, 2-Ph undergoes a clean photolysis that affords [(Ph)((o-Ph 2 P)C 6 H 4 ) 2 GePtCl] (1-Ph) and [(Cl)((o-Ph 2 P)C 6 H 4 ) 2 GePtCl](1-Cl) as confirmed by NMR spectroscopy. While the formation of 1-Ph results from the elimination of a chlorine equivalent from 2-Ph, the formation of 1-Cl indicates chlorobenzene elimination, which was confirmed and quantified using GC-MS. These results provide a unique example of a germanium-centered light-induced reduction process resulting in the ipso-chlorination of a phenylgermanium species.

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“…This chemistry was later expanded to the reactions of alkenes with R 3 Ge–GeR 3 and R 3 GeCOOH . Another general approach to alkylgermanes is transition-metal-catalyzed cross-coupling reactions . For example, the Oestreich group has recently reported a nickel-catalyzed Csp 3 –Ge coupling of alkyl–X with R 3 GeZnCl·2LiCl (Scheme a, path b) .…”

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confidence: 99%

Nickel-Catalyzed Reductive Csp³–Ge Coupling of Alkyl Bromides with Chlorogermanes

et al. 2022

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Reductive cross-coupling provides facile access to organogermanes, but it remains largely unexplored. Herein we report a nickel-catalyzed reductive Csp3–Ge coupling of alkyl bromides with chlorogermanes. This work has established a new method for producing alkylgermanes. The reaction proceeds under very mild conditions and tolerates various functionalities including ether, alcohol, alkene, nitrile, amine, ester, phosphonates, amides, ketone, and aldehyde. The application of this method to the modification of bioactive molecules is demonstrated.

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Pd/Ni-Catalyzed Germa-Suzuki coupling via dual Ge–F bond activation

Abstract: Pd/Ni->Ge-F interactions supported by phosphine-chelation were found to trigger dual activation of Ge-F bonds under mild conditions. This makes fluoro germanes suitable partners for catalytic Ge-C cross-coupling and enables Germa-Suzuki...

Cited by 18 publications

References 46 publications

Alkali Metal Adducts of an Iron(0) Complex and Their Synergistic FLP-Type Activation of Aliphatic C–X Bonds

Alkali Metal Adducts of an Iron(0) Complex and Their Synergistic FLP-Type Activation of Aliphatic C–X Bonds

Photoreductive Elimination of PhCl Across the Dinuclear Core of a [GePt]^VI Complex

Nickel-Catalyzed Reductive Csp³–Ge Coupling of Alkyl Bromides with Chlorogermanes

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Pd/Ni-Catalyzed Germa-Suzuki coupling via dual Ge–F bond activation

Abstract: Pd/Ni->Ge-F interactions supported by phosphine-chelation were found to trigger dual activation of Ge-F bonds under mild conditions. This makes fluoro germanes suitable partners for catalytic Ge-C cross-coupling and enables Germa-Suzuki...

Cited by 18 publications

References 46 publications

Alkali Metal Adducts of an Iron(0) Complex and Their Synergistic FLP-Type Activation of Aliphatic C–X Bonds

Alkali Metal Adducts of an Iron(0) Complex and Their Synergistic FLP-Type Activation of Aliphatic C–X Bonds

Photoreductive Elimination of PhCl Across the Dinuclear Core of a [GePt]VI Complex

Nickel-Catalyzed Reductive Csp3–Ge Coupling of Alkyl Bromides with Chlorogermanes

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About

Photoreductive Elimination of PhCl Across the Dinuclear Core of a [GePt]^VI Complex

Nickel-Catalyzed Reductive Csp³–Ge Coupling of Alkyl Bromides with Chlorogermanes