Electrochemical Synthesis of 1,2-Disilylethanes from α-Silylacetic Acids

The direct synthetic organic use of electricity is currently experiencing a renaissance. More synthetically oriented laboratories working in this area are exploiting both novel and more traditional concepts, paving the way to broader applications of this niche technology. As only electrons serve as reagents, the generation of reagent waste is efficiently avoided. Moreover, stoichiometric reagents can be regenerated and allow a transformation to be conducted in an electrocatalytic fashion. However, the application of electroorganic transformations is more than minimizing the waste footprint, it rather gives rise to inherently safe processes, reduces the number of steps of many syntheses, allows for milder reaction conditions, provides alternative means to access desired structural entities, and creates intellectual property (IP) space. When the electricity originates from renewable resources, this surplus might be directly employed as a terminal oxidizing or reducing agent, providing an ultra‐sustainable and therefore highly attractive technique. This Review surveys recent developments in electrochemical synthesis that will influence the future of this area.

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“…The current efficiency was relatively high, and current densities of 250 mA cm −2 were applied (Scheme 17). 69 …”

Section: Kolbe Electrolysismentioning

confidence: 99%

Electrifying Organic Synthesis

et al. 2018

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“…Since it has been known that a silyl groups stabilize alkyl radicals, this effect contradicts with the one exerted by an alkyl substituent, which favors carbenium ion stabilization, leading to non-Kolbe products via follow up reactions with nucleophiles. Therefore, it is not surprising that no Kolbe 'dimer' was detected from the electrolysis of Ph 2 MeSiCH(n-Pr)CO 2 H (XIII) at a Pt anode, unlike the a-unalkylated acids [5]. It afforded 35% of a non-Kolbe product, as shown in Scheme 9, and 50% of recovered starting material.…”

Section: Anodic Oxidation Of Ph 2 Mesich(r)co 2 H [R ¼ Allyl (Xi); Bementioning

confidence: 99%

“…Recently we have shown that they could also be useful precursors for the synthesis of 1,2-disilylethanes in good yields by their electrochemical oxidation [4,5].…”

Section: Introductionmentioning

confidence: 99%

Synthesis of α-germyl and α-silylcarboxylic acids and selected electrochemical oxidations

Rakovshik

Shtelman

Becker

2012

Journal of Organometallic Chemistry

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“…The current efficiency was relatively high, and current densities of 250 mA cm À2 were applied (Scheme 17). [69] Seebach and co-workers developed anon-Kolbe electrolysis with protected 4-hydroxyproline derivatives to obtain the corresponding methoxy-substituted products in high yields for follow-up reactions (Scheme 18). [70] Markó and co-workers developed ap rocess to access ketones by twofold oxidative decarboxylation of disubstituted malonic acids.…”

Section: Scheme 14mentioning

confidence: 99%

“…Kolbe dimerization of a-silylacetic acids. [69] Scheme 18. Non-Kolbec onversion of an enantiomerically pure protected 4-hydroxyproline.…”

Section: Scheme 14mentioning

confidence: 99%

Elektrifizierung der organischen Synthese

et al. 2018

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Die direkte Nutzung von Elektrizität für die organische Synthese erlebt derzeit eine Renaissance. Von den eher syntheseorientierten Laboratorien, die auf diesem Gebiet arbeiten, werden neuartige oder althergebrachte Konzepte genutzt, um den Weg von der Nischentechnologie zu breiteren Anwendungen zu ebnen. Da nur Elektronen als Reagens genutzt werden, wird die Bildung von Abfallreagentien effizient vermieden. Darüber hinaus können stöchiometrische Reagentien regeneriert werden und ermöglichen eine elektrokatalysierte Umsetzung. Die Anwendung von elektroorganischen Transformationen ist jedoch mehr als nur die Minimierung des Abfallaufkommens; sie führt vielmehr zu inhärent sicheren Prozessen, zur Abkürzung vieler Synthesestufen, zu milderen Reaktionsbedingungen, zu alternativen Zugängen zu gewünschten Struktureinheiten sowie zur Schaffung neuer Bereiche für geistiges Eigentum (Patente). Wenn die verwendete Elektrizität aus regenerativen Ressourcen stammt, kann dieser Stromüberschuss direkt als terminales Oxidations‐ oder Reduktionsmittel eingesetzt werden, was eine äußerst nachhaltige und damit hochattraktive Technologie darstellt. Dieser Aufsatz gibt einen Überblick über die jüngsten Entwicklungen auf dem Gebiet der elektrochemischen Synthese, welche die Zukunft dieses stark aufstrebenden Gebietes beeinflussen werden.

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Electrochemical Synthesis of 1,2-Disilylethanes from α-Silylacetic Acids

Cited by 22 publications

References 46 publications

Electrifying Organic Synthesis

Electrifying Organic Synthesis

Synthesis of α-germyl and α-silylcarboxylic acids and selected electrochemical oxidations

Elektrifizierung der organischen Synthese

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