Toward Polynuclear Ru–Cu Catalytic Dehydrogenative C–N Bond Formation, on the Reactivity of Carbazoles

Louillat, Marie‐Laure; Patureau, Frédéric W.

doi:10.1021/ol303216u

Cited by 87 publications

(49 citation statements)

References 87 publications

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“…In an early 2013 communication, some of us delivered preliminary results about a Ru/Cu co‐catalyzed dehydrogenative homo‐coupling of two carbazoles to form a unique C1−N bicarbazole product (Scheme ) . This early method, however, suffered from very low turn‐over‐frequencies (TOFs), thereby requiring up to two weeks of reaction time.…”

Section: Methodsmentioning

confidence: 99%

Accelerated Ru–Cu Trinuclear Cooperative C−H Bond Functionalization of Carbazoles: A Kinetic and Computational Investigation

Jones¹,

Rank²,

Becker³

et al. 2018

Chemistry A European J

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The mechanism of a trinuclear cooperative dehydrogenative C−N bond‐forming reaction is investigated in this work, which avoids the use of chelate‐assisting directing groups. Two new highly efficient Ru/Cu co‐catalyzed systems were identified, allowing orders of magnitude greater TOFs than the previous state of the art. In‐depth kinetic studies were performed in combination with advanced DFT calculations, which reveal a decisive rate‐determining trinuclear Ru–Cu cooperative reductive elimination step (CRE).

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Section: Methodsmentioning

confidence: 99%

Accelerated Ru–Cu Trinuclear Cooperative C−H Bond Functionalization of Carbazoles: A Kinetic and Computational Investigation

Jones¹,

Rank²,

Becker³

et al. 2018

Chemistry A European J

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“…Diese beinhalten die Anwendung der MCV auf eine metallkatalysierte dehydrierende C-N-Bindungsbildung, [67] eine Rhkatalysierte Hydroacylierung, [68] organometallische Assoziationen mit Cyclodextrinen [69] und die Koordination von Pinzettenliganden an Pd. Diese beinhalten die Anwendung der MCV auf eine metallkatalysierte dehydrierende C-N-Bindungsbildung, [67] eine Rhkatalysierte Hydroacylierung, [68] organometallische Assoziationen mit Cyclodextrinen [69] und die Koordination von Pinzettenliganden an Pd.…”

Section: Protokoll Der Literaturrechercheunclassified

Methode der kontinuierlichen Variation: Verwendung von Job‐Plots zur Untersuchung molekularer Assoziationen in der metallorganischen Chemie

et al. 2013

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Dieser Aufsatz beschreibt Anwendungen der Methode der kontinuierlichen Variation (MCV oder Job‐Plots) auf Fragen der metallorganischen Chemie. Die MCV bietet qualitative und quantitative Einblicke in die Stöchiometrien, die der Assoziation von m Molekülen A und n Molekülen B zur Bildung von AmBn zugrunde liegen. Auch komplexere Fälle von Metallclustern und Aggregaten sind beschreibbar. Job‐Plots, in denen Reaktionsgeschwindigkeiten verfolgt werden, liefern relative Stöchiometrien geschwindigkeitsbestimmender Übergangsstrukturen. In einer speziellen Variante werden von den Liganden oder dem Lösungsmittel abhängige Reaktionsgeschwindigkeiten in Grundzustands‐ und Übergangszustandsbeiträge aufgegliedert, was einen Einblick in die vollständige Reaktionskoordinate mithilfe eines einzigen Job‐Plots ermöglicht. Die Lücken in der Literatur werden aufgezeigt und besprochen.

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“…On the other hand, the transition-metal-catalyzed sp 2 C-H amination reaction is one of the most demanding procedures to form C-N bonds [36,37]. In recent years, various late transition metal catalysts such as Pd [38][39][40][41], Ru [42], Rh [43], Ir [44], and Cu [45] have been applied in sp 2 C-H bond amination. Within this methodology, Pd-catalyzed intramolecular aza-Wacker-type oxidative reactions represent one crucial route to produce a range of 5-membered N-containing heterocycles [46][47][48][49][50][51].…”

Section: Introductionmentioning

confidence: 99%

Practical Pd(TFA)2-Catalyzed Aerobic [4+1] Annulation for the Synthesis of Pyrroles via “One-Pot” Cascade Reactions

Mang

Yang

et al. 2016

Catalysts

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Abstract:The Pd(TFA) 2 -catalyzed [4+1] annulation of chained or cyclic α-alkenyl-dicarbonyl compounds and unprotected primary amines for "one-pot" synthesis of pyrroles is reported here. Enamination and amino-alkene were involved in this practical and efficient tandem reaction. The annulation products were isolated in moderate to excellent yields with O 2 as the terminal oxidant under mild conditions. In addition, this method was applied to synthesize highly regioselective aminomethylated and di(1H-pyrrol-3-yl)methane products.

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Toward Polynuclear Ru–Cu Catalytic Dehydrogenative C–N Bond Formation, on the Reactivity of Carbazoles

Abstract: The cooperative action of Ru and Cu catalysts enables direct polynuclear C-H and N-H activation for the dehydrogenative N-carbazolation of carbazoles, selectively at the C1 position. Initial mechanistic experiments are presented and discussed.

Cited by 87 publications

References 87 publications

Accelerated Ru–Cu Trinuclear Cooperative C−H Bond Functionalization of Carbazoles: A Kinetic and Computational Investigation

Accelerated Ru–Cu Trinuclear Cooperative C−H Bond Functionalization of Carbazoles: A Kinetic and Computational Investigation

Methode der kontinuierlichen Variation: Verwendung von Job‐Plots zur Untersuchung molekularer Assoziationen in der metallorganischen Chemie

Practical Pd(TFA)2-Catalyzed Aerobic [4+1] Annulation for the Synthesis of Pyrroles via “One-Pot” Cascade Reactions

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