Anodic oxidation of α-silylacetic acids: Effects of anode material, current density and concentration on competing decarboxylation and desilylation processes

Brakha, Libi; Becker, James Y.

doi:10.1016/j.electacta.2012.05.089

Cited by 9 publications

(6 citation statements)

References 21 publications

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“…The ensuing alkyl radical then dimerizes to forge a C–C bond. Development and applications of Kolbe electrolysis before 2000 have been reviewed; ,, more recently, this classical process has been utilized to synthesize benzathine, construct bis -phosphine oxide ligands, and dimerize silylacetic acids − and fatty acids . The mixed-Kolbe reaction, wherein a heterodimerization between two different alkyl carboxylic acids occurs, is less commonan excess of one acid component is often necessary to favor the cross-coupling product .…”

Section: Anodic Oxidationmentioning

confidence: 99%

Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance

2017

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Section: Anodic Oxidationmentioning

confidence: 99%

Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance

2017

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“…[27,29,30,[46][47][48][49] Accordingly,a ni ncreased yield of Kolbe product demands ah igher electric poweri nput (P el )c ompared to non-Kolbe product formation, as the power consumption of an www.chemsuschem.org electrochemical cell is definedb yt he product of the current (i) and the cell voltage (E cell )a ss hown in Equation (1). [27,29,30,[46][47][48][49] Accordingly,a ni ncreased yield of Kolbe product demands ah igher electric poweri nput (P el )c ompared to non-Kolbe product formation, as the power consumption of an www.chemsuschem.org electrochemical cell is definedb yt he product of the current (i) and the cell voltage (E cell )a ss hown in Equation (1).…”

Section: Considerations On Supporting Electrolytes For Kolbe Electrolmentioning

confidence: 99%

“…As high current densities are said to promote Kolbe product formation, [27,29,30,[46][47][48][49] energy-friendly Kolbe electrolysis should be performed at high electrolytic conductivities that are achieved either by addings upportinge lectrolytes or increasing the concentration of the reactant. Therefore, the influence of type and concentrationo fs upportinge lectrolyte was further evaluated.…”

Section: Mechanistic Study On Kolbe Electrolysis In Aqueous Solutionsmentioning

confidence: 99%

“…Literature suggestst hat high current densities (e.g., 0.25 Acm À2 )p romote Kolbe product formation,w hereas low current densities preferably lead to non-Kolbep roducts. [27,29,30,[46][47][48][49] Accordingly,a ni ncreased yield of Kolbe product demands ah igher electric poweri nput (P el )c ompared to non-Kolbe product formation, as the power consumption of an www.chemsuschem.org electrochemical cell is definedb yt he product of the current (i) and the cell voltage (E cell )a ss hown in Equation (1). Applying Ohm's law,t he electric powern eededt od rive ag iven i depends on the total resistance of the cell R total [Eq.…”

Section: Considerations On Supporting Electrolytes For Kolbe Electrolmentioning

confidence: 99%

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The Dilemma of Supporting Electrolytes for Electroorganic Synthesis: A Case Study on Kolbe Electrolysis

Stang

Harnisch

2015

ChemSusChem

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Remarkably, coulombic efficiency (CE, about 50 % at 1 Farad equivalent), and product composition resulting from aqueous Kolbe electrolysis are independent of reactor temperature and initial pH value. Although numerous studies on Kolbe electrolysis are available, the interrelations of different reaction parameters (e.g., acid concentration, pH, and especially electrolytic conductivity) are not addressed. A systematic analysis based on cyclic voltammetry reveals that solely the electrolytic conductivity impacts the current-voltage behavior. When using supporting electrolytes, not only their concentration, but also the type is decisive. We show that higher concentrations of KNO3 result in reduced CE and thus in significant increase in electric energy demand per converted molecule, whereas Na2 SO4 allows improved space-time yields. Pros and cons of adding supporting electrolytes are discussed in a final cost assessment.

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“…Since 2000, this strategy has been applied in the synthesis of bisphosphine oxide ligands, to synthesize benzathine, and to dimerize silylacetic acids − and fatty acids. , Despite the significance, the selectivity control of a mixed-Kolbe reaction between two different alkyl carboxylic acids is still a challenge, in which an excess of one partner is required for the cross-coupling product . In 2002, a mixed-Kolbe electrolysis was developed by Renaud and co-workers to synthesize nephromopsinic, phaseolinic, and dihydropertusaric acids (Scheme ).…”

Section: Cleavage Of C–c Single Bondsmentioning

confidence: 99%

Electrochemical Oxidation Induced Selective C–C Bond Cleavage

2020

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Selective C−C bond cleavage under mild conditions can serve as a valuable tool for organic syntheses and macromolecular degradation. However, the conventional chemical methods have largely involved the use of noble transition-metal catalysts as well as the stoichiometric and perhaps environmentally unfriendly oxidants, compromising the overall sustainable nature of C−C transformation chemistry. In this regard, electrochemical C−C bond cleavage has been identified as a sustainable and scalable strategy that employs electricity to replace byproduct-generating chemical reagents. To date, the progress made in this area has mainly relied on Kolbe electrolysis and related processes. Encouragingly, more and more examples of the cleavage of C−C bonds via other maneuvers have recently been developed. This review provides an overview on the most recent and significant developments in electrochemically oxidative selective C−C bond cleavage, with an emphasis on both synthetic outcomes and reaction mechanisms, and it showcases the innate advantages and exciting potentials of electrochemical synthesis. CONTENTS 1. Introduction 485 2. Cleavage of C−C Single Bonds 486 2.1. Kolbe Electrolysis and Related Processes 486 2.2. Cleavage of C sp 3 −C(O) Bonds 490 2.3. Cleavage of Vicinal Difunctional Compounds' C−C Bonds 492 2.4. Cleavage of C sp 2 −C Bonds 493 2.5. Cleavage of Bridged and Strained Cyclic C− C Bonds 495 2.6. Cleavage of C−C Bonds via Migration Reactions 497 3. Cleavage of CC Double Bonds 497 3.1. Oxygenation of CC to Carbonyl Compounds 497 3.2. Oxygenation of CC to Carboxyl Compounds 500 4. Conclusion and

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Anodic oxidation of α-silylacetic acids: Effects of anode material, current density and concentration on competing decarboxylation and desilylation processes

Cited by 9 publications

References 21 publications

Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance

Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance

The Dilemma of Supporting Electrolytes for Electroorganic Synthesis: A Case Study on Kolbe Electrolysis

Electrochemical Oxidation Induced Selective C–C Bond Cleavage

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