Direct Functionalization of Tetrahydrofuran and 1,4‐Dioxane: Nickel‐Catalyzed Oxidative C(sp<sup>3</sup>)H Arylation

Liu, Dong; Liu, Chao; Li, Heng; Lei, Aiwen

doi:10.1002/ange.201300459

Cited by 67 publications

(30 citation statements)

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“…Shortly after, a nickel-catalyzed oxidative arylation of ortho-C(sp 3 )ÀH bonds that are adjacent to the oxygen atom of tetrahydrofuran (THF) or 1,4-dioxane with aryl boronic acids was reported by the same group (Scheme 4). [10] THF and 1,4dioxane moieties frequently occur as part of the structures of important organic compounds. [11] However, direct functionalization of the THF or 1,4-dioxane rings is a challenging task owing to a lack of reactivity.…”

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confidence: 99%

Oxidative Catalytic Coupling Reactions: Selective Formation of CC and CX Bonds Using Radical Processes

2013

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Oxidative Catalytic Coupling Reactions: Selective Formation of CC and CX Bonds Using Radical Processes

2013

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“…[36,37] Alle bisher diskutierten Beispiele erforderten vorfunktionalisierte Substrate.M olander und Mitarbeiter entwickelten kürzlich eine photochemische C-H-Arylierung,d ie über C(sp 3 )-H-Bindungen durch Nickel katalysiert wird. [38] Der Tr iplett-Zustand eines Diarylketons kann C(sp 3 )-H-Bindungen über den H-Atom-Transfer (HAT) aktivieren, [39] [40] wie die Verwendung der stabilen Arylbromide anstelle von Arylboronsäuren. Beide Ansätze erfordern jedoch die Verwendung des C(sp 3 )-H-Partners in großem Überschuss,z.B.als Lçsungsmittel in der Reaktion.…”

Section: Bildung Von Produkten Mit C(sp 3 )-C(sp 2 )-Bindungenunclassified

Photokatalyse mit sichtbarem Licht: Welche Bedeutung hat sie für die organische Synthese?

et al. 2018

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Die Photokatalyse mit sichtbarem Licht hat sich im letzten Jahrzehnt zu einer breit angewandten Methode in der organischen Synthese entwickelt. Für viele wichtige Reaktionen, wie Kreuzkupplungen, α‐Amino‐Funktionalisierungen, Cycloadditionen, ATRA‐Reaktionen oder Fluorierungen, wurden photokatalytische Varianten berichtet. Um Chemiker bei der Auswahl photokatalytischer Methoden für ihre Synthesen zu unterstützen, vergleichen wir in diesem Aufsatz klassische und photokatalytische Verfahren für ausgewählte Reaktionsklassen und zeigen deren Vorteile und Grenzen auf. In vielen Fällen verlaufen die photokatalytischen Reaktionen unter milderen Reaktionsbedingungen, typischerweise bei Raumtemperatur, und stöchiometrische Reagenzien werden durch einfache Oxidanzien oder Reduktionsmittel wie Luft, Sauerstoff oder Amine ersetzt. Beeinflusst die Photokatalyse mit sichtbarem Licht die organische Synthese? Die Aussicht, Elektronen zu Substraten und Zwischenprodukten hin‐ und herzuschieben oder Energie selektiv durch einen sichtbares Licht absorbierenden Photokatalysatoren zu übertragen, verspricht die aktuellen Verfahren in der Radikalchemie zu verbessern und neue Wege durch den Zugang zu reaktiven, bisher unbekannten Spezies zu erschließen, insbesondere durch das Zusammenspiel von Photokatalyse mit der Organo‐ oder Metallkatalyse.

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“…Our recent research on nickel-catalyzed oxidative cross-coupling of arylboronic acids with ethers might demonstrate the possibility of this reaction pathway. 26 The transformation achieves α-C−H arylation of THF or dioxane with arylboronic acids in the presence of Ni(acac) 2 also is suitable for other C sp 3 −H compounds such as the Nmethyl group of N,N-dimethylaniline, N,N-dimethylacetamide, and N-methyl pyrrole, which were arylated smoothly to afford the desired products in moderate to good yields.…”

Section: Model IV In Radical Oxidativementioning

confidence: 99%

Recent Advances of Transition-Metal Catalyzed Radical Oxidative Cross-Couplings

2014

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CONSPECTUS: Oxidative cross-coupling reactions between two nucleophiles are a powerful synthetic strategy to synthesize various kinds of functional molecules. Along with the development of transition-metal-catalyzed oxidative cross-coupling reactions, chemists are applying more and more first-row transition metal salts (Fe, Co, etc.) as catalysts. Since first-row transition metals often can go through multiple chemical valence changes, those oxidative cross-couplings can involve single electron transfer processes. In the meantime, chemists have developed diverse mechanistic hypotheses of these types of reactions. However, none of these hypotheses have led to conclusive reaction pathways until now. From studying both our own work and that of others in this field, we believe that radical oxidative cross-coupling reactions can be classified into four models based on the final bond formations. In this Account, we categorize and summarize these models. In model I, one of the starting nucleophiles initially loses one electron to generate its corresponding radical under oxidative conditions. Then, bond formations between this radical and another nucleophile create a new radical, [Nu(1)-Nu(2)](•), followed by a further radical oxidation step to generate the cross-coupling product. The radical oxidative alkenylation with olefin, radical oxidative arylative-annulation, and radical oxidative amidation are examples of this model. In model II, one of the starting nucleophiles loses its two electrons via two steps of single-electron-transfer to generate an electrophilic intermediate, followed by a direct bond formation with the other nucleophile. For example, the oxidative C-O coupling of benzylic sp(3) C-H bonds with carboxylic acids and oxidative C-N coupling of aldehydes with amides are members of this model group. For model III, both nucleophiles are oxidized to their corresponding radicals. Then, the radicals combine to form the final coupling product. The dioxygen-involved radical oxidative cross-couplings between sulfinic acids and olefins or alkynes belong to this bond formation model. Lastly, in model IV, one nucleophile loses two electrons to generate an electrophilic intermediate, while the other nucleophile loses one electron to generate a radical. Then, a bond forms between the cation and the radical to generate a cationic radical, followed by a one-electron reduction to afford the final coupling product. The oxidative coupling between arylboronic acids and simple ethers was classified in this model. At the current stage, there are only a few examples presented for models III and IV, but they represent two types of potentially important transformations. More and more examples of these two models will be developed in the future.

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Direct Functionalization of Tetrahydrofuran and 1,4‐Dioxane: Nickel‐Catalyzed Oxidative C(sp³)H Arylation

Abstract: Nimm Nickel: In der Titelreaktion, die vermutlich nach einem radikalischen Mechanismus verläuft, konnten substituierte Arylboronsäuren mit den C(sp3)‐H‐Bindungen einfacher Ether gekuppelt werden. Die Methode liefert die α‐arylierten Ether als Produkte. FG=funktionelle Gruppe.

Cited by 67 publications

References 43 publications

Oxidative Catalytic Coupling Reactions: Selective Formation of CC and CX Bonds Using Radical Processes

Oxidative Catalytic Coupling Reactions: Selective Formation of CC and CX Bonds Using Radical Processes

Photokatalyse mit sichtbarem Licht: Welche Bedeutung hat sie für die organische Synthese?

Recent Advances of Transition-Metal Catalyzed Radical Oxidative Cross-Couplings

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Direct Functionalization of Tetrahydrofuran and 1,4‐Dioxane: Nickel‐Catalyzed Oxidative C(sp3)H Arylation

Abstract: Nimm Nickel: In der Titelreaktion, die vermutlich nach einem radikalischen Mechanismus verläuft, konnten substituierte Arylboronsäuren mit den C(sp3)‐H‐Bindungen einfacher Ether gekuppelt werden. Die Methode liefert die α‐arylierten Ether als Produkte. FG=funktionelle Gruppe.

Cited by 67 publications

References 43 publications

Oxidative Catalytic Coupling Reactions: Selective Formation of CC and CX Bonds Using Radical Processes

Oxidative Catalytic Coupling Reactions: Selective Formation of CC and CX Bonds Using Radical Processes

Photokatalyse mit sichtbarem Licht: Welche Bedeutung hat sie für die organische Synthese?

Recent Advances of Transition-Metal Catalyzed Radical Oxidative Cross-Couplings

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Direct Functionalization of Tetrahydrofuran and 1,4‐Dioxane: Nickel‐Catalyzed Oxidative C(sp³)H Arylation