Carboxylate‐Assisted Ruthenium(II)‐Catalyzed Hydroarylations of Unactivated Alkenes through C–H Cleavage

Schinkel, Marvin; Marek, Ilan; Ackermann, Lutz

doi:10.1002/anie.201208446

Cited by 165 publications

(64 citation statements)

References 66 publications

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“…[1] In particular,c atalyzed hydroarylations of alkenes by C À Ha ctivation are instrumental for the development of atom-economical CÀHa lkylations.F ull control of regioselectivity is paramount for the development of synthetically useful CÀHa dditions onto unbiased alkenes. [4][5][6][7] In stark contrast, branching hydroarylations of unactivated alkenes continues to be scarce,w ith very recent progress being elegantly achieved by Bower using precious iridium complexes. [4][5][6][7] In stark contrast, branching hydroarylations of unactivated alkenes continues to be scarce,w ith very recent progress being elegantly achieved by Bower using precious iridium complexes.…”

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confidence: 99%

Full Selectivity Control in Cobalt(III)‐Catalyzed C−H Alkylations by Switching of the C−H Activation Mechanism

et al. 2017

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Selectivity control in hydroarylation-based C-H alkylation has been dominated by steric interactions. A conceptually distinct strategy that exploits the programmed switch in the C-H activation mechanism by means of cobalt catalysis is presented, which sets the stage for convenient C-H alkylations with unactivated alkenes. Detailed mechanistic studies provide compelling evidence for a programmable switch in the C-H activation mechanism from a linear-selective ligand-to-ligand hydrogen transfer to a branched-selective base-assisted internal electrophilic-type substitution.

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confidence: 99%

Full Selectivity Control in Cobalt(III)‐Catalyzed C−H Alkylations by Switching of the C−H Activation Mechanism

et al. 2017

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“…However, most are limited to reactions with activated alkenes, such as α,β‐unsaturated carbonyl compounds, styrene derivatives and norbornene, or non‐isomerizable alkenes, such as ethylene, tert ‐butylethylene and vinylsilanes. The hydroarylation reaction of simple non‐activated 1‐alkenes, which is applicable to a wide range of substrates, continues to remain a challenging issue . In most cases, the hydroarylation of non‐activated 1‐alkenes is applicable only to the reactive heteroaromatic C−H bonds or to a limited range of 1‐alkenes.…”

Section: Methodsmentioning

confidence: 99%

Rhodium‐Catalyzed Alkylation of C−H Bonds in Aromatic Amides with Non‐activated 1‐Alkenes: The Possible Generation of Carbene Intermediates from Alkenes

Yamaguchi

Natsui

Shibata

et al. 2019

Chemistry A European J

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The alkylation of C−H bonds (hydroarylation) in aromatic amides with non‐activated 1‐alkenes using a rhodium catalyst and assisted by an 8‐aminoquinoline directing group is reported. The addition of a carboxylic acid is crucial for the success of this reaction. The results of deuterium‐labeling experiments indicate that one of deuterium atoms in the alkene is missing, suggesting that the reaction does not proceed through the commonly accepted mechanism for C−H alkylation reactions. Instead the reaction is proposed to proceed through a carbene mechanism. The carbene mechanism is also supported by preliminary DFT calculations.

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“…Die repräsentativsten Beispiele sind in Schema 37 gezeigt. [162] Pyridine,Imidazole und Pyrazole fungierten als effiziente dirigierende Gruppen zur Herstellung der linearen ortho-alkylierten Produkte in hervorragenden Ausbeuten und Selektivitäten ohne konkurrierende Zweifachal- [161] Ackermann et al demonstrierten, dass Ruthenium(II)-Komplexe effizient die Alkylierung ähnlicher Substrate in Gegenwart eines sperrigen Carboxylats zur Unterstützung der Spaltung der C-H-Bindung katalysieren (Schema 37, Einschub * 3).…”

Section: Alkylierung Mit Alkenenunclassified

“…Die C2-Alkylierung von N-(2-Pyri(mi)dyl)indolen mit Alkenen kann von diversen Metallen katalysiert werden, einschließlich Ruthenium, [162] Cobalt, [168c, 192] Mangan [193] und Schema 39. Palladium-und rhodiumkatalysierte ortho-Alkylierung von 2-(N-Heteroaryl)arenen mit Alkylborreagentien.…”

Section: Alkylierung Mit Alkenenunclassified

Jenseits von Friedel und Crafts: dirigierte Alkylierung von C‐H‐Bindungen in Arenen

Evano

Theunissen

2019

Angewandte Chemie

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Die Alkylierung von Arenen ist eine der grundlegendsten Transformationen in der chemischen Synthese und führt in vielen wissenschaftlichen Bereichen zu privilegierten Molekülgerüsten. Klassische Methoden für die Einführung von Alkylgruppen in Arene beruhen zumeist auf der Friedel‐Crafts‐Reaktion, Radikaladditionen, Metallierungen oder Präfunktionalisierungen von Arenen; die Anwendungsbreite, Effizienz und Selektivität dieser Methoden sind jedoch begrenzt. Außerdem bauen sie auf der inhärenten Reaktivität des Ausgangsarens auf, die die Alkylierung in einer bestimmten Position bevorzugt und die Einführung von Alkylketten an anderen Stellen wesentlich schwieriger macht. Dieses Problem kann durch die Verwendung einer dirigierenden Gruppe angegangen werden, die in Gegenwart eines Metallkatalysators die regioselektive Alkylierung einer C‐H‐Bindung vereinfacht. Diese dirigierten Alkylierungen von C‐H‐Bindungen in Arenen werden im vorliegenden Aufsatz zusammengefasst.

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Carboxylate‐Assisted Ruthenium(II)‐Catalyzed Hydroarylations of Unactivated Alkenes through C–H Cleavage

Cited by 165 publications

References 66 publications

Full Selectivity Control in Cobalt(III)‐Catalyzed C−H Alkylations by Switching of the C−H Activation Mechanism

Full Selectivity Control in Cobalt(III)‐Catalyzed C−H Alkylations by Switching of the C−H Activation Mechanism

Rhodium‐Catalyzed Alkylation of C−H Bonds in Aromatic Amides with Non‐activated 1‐Alkenes: The Possible Generation of Carbene Intermediates from Alkenes

Jenseits von Friedel und Crafts: dirigierte Alkylierung von C‐H‐Bindungen in Arenen

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