Continuous in situ electrogenaration of a 2-pyrrolidone anion in a microreactor: application to highly efficient monoalkylation of methyl phenylacetate

Matsumura, Yoshihito; Kakizaki, Yoshinobu; Tateno, Hiroyuki; Kashiwagi, Tsuneo; Yamaji, Yoshiyuki; Atobe, Mahito

doi:10.1039/c5ra19286b

Cited by 15 publications

(23 citation statements)

References 26 publications

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“…In this regard, there are two similar examples. In the first one, a process was designed for the α‐alkylation of methyl phenylacetate, in which 2‐pyrrolidone was electroreduced in flow, with the formed anion acting as a base. The base could abstract the α‐proton of methyl phenylacetate, thereby forming a carbanion which reacted subsequently with iodomethane to afford the methylated product (Scheme , top).…”

Section: Electrochemical Reactions In Flow Cellssupporting

confidence: 63%

“…In addition to oxidations,s everal electroreduction processes in flow cells have been reported, most of them developed by Atobe and co-workers.I narecent example, they performed the electrochemically assisted reduction of toluene to the corresponding methylcyclohexane by using hydrogen as ar educing agent. [146] Thef ormation of anions prior to electroreduction has also been utilized as au seful method in the development of some processes.Inthis regard, there are two similar examples.Inthe first one,aprocess was designed for the a-alkylation of methyl phenylacetate, [147] in which 2-pyrrolidone was electroreduced in flow,w ith the formed anion acting as abase.The base could abstract the aproton of methyl phenylacetate,thereby forming acarbanion which reacted subsequently with iodomethane to afford the methylated product (Scheme 52, top). In the second example, the pyrrolidone anion was used to deprotonate chloroform to Scheme 46.…”

Section: Electroreductions In Flow Cellsmentioning

confidence: 99%

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Modern Electrochemical Aspects for the Synthesis of Value‐Added Organic Products

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The use of electricity instead of stoichiometric amounts of oxidizers or reducing agents in synthesis is very appealing for economic and ecological reasons, and represents a major driving force for research efforts in this area. To use electron transfer at the electrode for a successful transformation in organic synthesis, the intermediate radical (cation/anion) has to be stabilized. Its combination with other approaches in organic chemistry or concepts of contemporary synthesis allows the establishment of powerful synthetic methods. The aim in the 21st Century will be to use as little fossil carbon as possible and, for this reason, the use of renewable sources is becoming increasingly important. The direct conversion of renewables, which have previously mainly been incinerated, is of increasing interest. This Review surveys many of the recent seminal important developments which will determine the future of this dynamic emerging field.

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Section: Electrochemical Reactions In Flow Cellssupporting

confidence: 63%

Section: Electroreductions In Flow Cellsmentioning

confidence: 99%

Modern Electrochemical Aspects for the Synthesis of Value‐Added Organic Products

et al. 2018

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“…[142] Schema 49. [147] Durch Abstraktion eines a-Protons vom Methylphenylacetat durch diese generierte Base kommt es zur Bildung eines Carbanions.A nschließend reagiert dieses mit Iodmethan zum methylierten Produkt (Schema 52, oben). [143] Schema 50.…”

Section: Elektrochemische Reduktion In Durchflusselektrolysezellenunclassified

“…In diesem Kontext gibt es zwei ähnliche Beispiele: Im ersten Beispiel wurde die a-Alkylierung von Methylphenylacetat durchgeführt, wobei 2-Pyrrolidon elektrochemisch und kontinuierlich reduziert wurde.D as gebildete Anion wirkt dabei als Base. [147] Durch Abstraktion eines a-Protons vom Methylphenylacetat durch diese generierte Base kommt es zur Bildung eines Carbanions.A nschließend reagiert dieses mit Iodmethan zum methylierten Produkt (Schema 52, oben). Im zweiten Beispiel wurde die Bildung des Pyrrolidonanions genutzt, um durch Deprotonierung von Chloroform das Trichlormethananion zu erhalten.…”

Section: Elektrochemische Reduktion In Durchflusselektrolysezellenunclassified

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Moderne Aspekte der Elektrochemie zur Synthese hochwertiger organischer Produkte

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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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Electrosynthesis in Laminar Flow Using a Flow Microreactor

Shida

Nakamura

Atobe

2021

The Chemical Record

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Electrosynthesis and microflow synthesis have become essential tools in their own rights in modern organic synthesis. In this personal account, we summarize our works on the integrated use of these techniques, i. e., electrosynthesis in a flow microreactor. Our group has developed an electrochemical microflow system composed of a pair of electrodes that face each other to form a micrometer‐scale gap for the flow path, through which solution passes in laminar flow. By the aid of laminar flow, unprecedented chemo‐ and electrochemical selectivity has been observed, which is not achievable with conventional batch‐type electrochemical cells. In addition, we showcase various unique electrochemical systems and reactions achieved with the flow microreactor, including self‐supported electrolysis, efficient paired electrolysis, in situ generation of active species and its flash use, the spaciotemporal control of electropolymerization, and combinatorial screening of the reaction conditions.

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Continuous in situ electrogenaration of a 2-pyrrolidone anion in a microreactor: application to highly efficient monoalkylation of methyl phenylacetate

Abstract: We have successfully demonstrated effective generation of an electrogenerated base (EGB) such as the 2-pyrrolidone anion and its rapid use for the following alkylation reaction in a flow microreactor system without the need for severe reaction conditions.

Cited by 15 publications

References 26 publications

Modern Electrochemical Aspects for the Synthesis of Value‐Added Organic Products

Modern Electrochemical Aspects for the Synthesis of Value‐Added Organic Products

Moderne Aspekte der Elektrochemie zur Synthese hochwertiger organischer Produkte

Electrosynthesis in Laminar Flow Using a Flow Microreactor

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