Reactions of a <i>N</i>-Acyliminium Ion Pool with Benzylsilanes. Implication of a Radical/Cation/Radical Cation Chain Mechanism Involving Oxidative C−Si Bond Cleavage

Maruyama, Tomokazu; Mizuno, Yusuke; Shimizu, Ikuo; Suga, Seiji; Yoshida, Jun

doi:10.1021/ja068589a

Cited by 88 publications

(38 citation statements)

References 45 publications

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“…91 However, that fluoride from the copper tetrafluoroborate acts as a nucleophile to assist heterolysis of the benzylic Ge-C bond rather than MeOH as proposed by Otsuji is not surprising (Scheme 5). 92 Encouraged by this photolysis result we subjected bis(2-naphthylmethyl)germane 18b to photolytic oxidation, this time using ∼4 equivalents of Cu(BF 4 ) 2 . For this substrate, the 1 H NMR of the crude reaction product showed the presence of 2-naphthylmethyl methyl ether 21 as expected but the remainder of the material gave signals that were significantly more complex than we would have anticipated for the Possible mechanism of photooxidation of (2-naphthylmethyl)germane 19.…”

Section: Resultsmentioning

confidence: 99%

The development of a ‘safety‐catch’ arylgermane for biaryl synthesis by palladium‐catalysed germyl‐stille cross‐coupling

Spivey

Gripton

Hannah

et al. 2007

Applied Organom Chemis

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The Pd(0) catalysed cross-coupling of arylgermanes with aryl bromides is shown to require at least two labile heteroatom ligands on the Ge centre to allow efficient nucleophilic activation by fluoride. Dichloroarylgermanes 7a and 7b are shown to cross-couple to a series of aryl bromides with moderate efficiency using activation by KF in DMF. Bis(2-naphthylmethyl)arylgermane 18b is identified as a 'safety-catch' precursor to this type of cross-coupling substrate. The 2-naphthylmethyl substituents can be removed via photolytic oxidation in the presence of Cu(BF 4 ) 2 and the resulting species, although not characterized, participates in cross-coupling using activation by TBAF in DMF.

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Section: Resultsmentioning

confidence: 99%

The development of a ‘safety‐catch’ arylgermane for biaryl synthesis by palladium‐catalysed germyl‐stille cross‐coupling

Spivey

Gripton

Hannah

et al. 2007

Applied Organom Chemis

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“…The method has been successfully applied to N-acyliminium ions, [10] alkoxycarbenium ions, [11] and diarylcarbenium ions. Thus, an aromatic compound is allowed to react with a radical cation of another aromatic compound, a species, which is generated and accumulated by low-temperature electrolysis.…”

Section: Tatsuya Morofuji Akihiro Shimizu and Jun-ichi Yoshida*mentioning

confidence: 99%

Metal‐ and Chemical‐Oxidant‐Free CH/CH Cross‐Coupling of Aromatic Compounds: The Use of Radical‐Cation Pools

2012

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Pool and couple: A method for oxidative C-H/C-H cross-coupling has been developed using "radical-cation pools". Aromatic compounds react with aryl radical cations, which are generated and accumulated by low-temperature electrolysis (see scheme). This method avoids both the nonselective oxidation of substrates and oxidation of products and effects the C-H/C-H cross-coupling of aromatic compounds without metal complexes and chemical oxidants.

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“…Anschließend wird ein Nukleophil zugesetzt, um das Produkt zu erhalten. [44] Eine weitere Mçglichkeit ist die Reduktion des Cation-Pools zum entsprechenden Radikal, wodurch es zur Rekombination kommt. B. N-Acyliminium-, [29,31] Alkoxycarbenium-, [32] Diarylcarbenium-, [33] Glykosyl-, [34] Silyl-, [35] Iod-, [36] Alkoxysulfonium-, [37,38] Benzylaminosulfonium-, [39] Aren- [40] Thioaren- [41] und auch Thioniumkationen.…”

Section: Die Cation-pool-methodeunclassified

Moderne Aspekte der Elektrochemie zur Synthese hochwertiger organischer Produkte

et al. 2018

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Die stoffliche Nutzung von Elektrizität anstelle stöchiometrischer Mengen an Oxidations‐ oder Reduktionsmitteln ist ökonomisch und ökologisch sehr attraktiv und stellt eine wichtige Triebkraft für die Forschungen in der Elektrosynthese dar. Um den Elektronentransfer an der Elektrode für eine organische Umsetzung zu nutzen, müssen die intermediär gebildeten Radikalspezies stabilisiert werden. Die Kombination der Elektrosynthese mit anderen Ansätzen der organischen Chemie oder aktuellen Synthesekonzepten ermöglicht die Entwicklung effizienter Synthesewege. Die zentrale Aufgabe des 21. Jahrhunderts besteht darin, möglichst wenig fossilen Kohlenstoff zu verwenden, weshalb die Nutzung erneuerbarer Energien immer wichtiger wird. Von steigendem Interesse ist auch die direkte Umsetzung erneuerbarer Rohstoffe, die zuvor hauptsächlich verbrannt wurden. Dieser Aufsatz gibt einen Überblick über viele der wichtigsten, zukunftsweisenden Entwicklungen der letzten Zeit, welche die Zukunft dieses sich rasch entwickelnden Feldes bestimmen werden.

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Reactions of a N-Acyliminium Ion Pool with Benzylsilanes. Implication of a Radical/Cation/Radical Cation Chain Mechanism Involving Oxidative C−Si Bond Cleavage

Cited by 88 publications

References 45 publications

The development of a ‘safety‐catch’ arylgermane for biaryl synthesis by palladium‐catalysed germyl‐stille cross‐coupling

The development of a ‘safety‐catch’ arylgermane for biaryl synthesis by palladium‐catalysed germyl‐stille cross‐coupling

Metal‐ and Chemical‐Oxidant‐Free CH/CH Cross‐Coupling of Aromatic Compounds: The Use of Radical‐Cation Pools

Moderne Aspekte der Elektrochemie zur Synthese hochwertiger organischer Produkte

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