Anodic oxidation of amides and lactams using N-hydroxyphthalimide as a mediator.

Masui, Masaichiro; Hara, Seijiro; Ozaki, Shigeko

doi:10.1248/cpb.34.975

Cited by 37 publications

(20 citation statements)

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“…The first synthetic application of PINO as a HAT catalyst was reported in 1977 by Grochowski . Reports from Masui in the 1980s demonstrated the ability to access PINO from NHPI using electrochemical methods. − Ishii demonstrated in 1995 that PINO could also be thermally accessed via autoxidation of NHPI, and subsequent studies showed that metal co-catalysts, such as Co II and Mn II , improve aerobic NHPI-catalyzed oxidation reactions. ,,,, …”

Section: Introductionmentioning

confidence: 99%

Tetramethylpiperidine N-Oxyl (TEMPO), Phthalimide N-Oxyl (PINO), and Related N-Oxyl Species: Electrochemical Properties and Their Use in Electrocatalytic Reactions

2018

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N-Oxyl compounds represent a diverse group of reagents that find widespread use as catalysts for the selective oxidation of organic molecules in both laboratory and industrial applications. While turnover of N-oxyl catalysts in oxidation reactions may be accomplished with a variety of stoichiometric oxidants, N-oxyl reagents have also been extensively used as catalysts under electrochemical conditions in the absence of chemical oxidants. Several classes of N-oxyl compounds undergo facile redox reactions at electrode surfaces, enabling them to mediate a wide range of electrosynthetic reactions. Electrochemical studies also provide insights into the structural properties and mechanisms of chemical and electrochemical catalysis by N-oxyl compounds. This review provides a comprehensive survey of the electrochemical properties and electrocatalytic applications of aminoxyls, imidoxyls, and related reagents, of which the two prototypical and widely used examples are 2,2,6,6-tetramethylpiperidine N-oxyl (TEMPO) and phthalimide N-oxyl (PINO).

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Section: Introductionmentioning

confidence: 99%

Tetramethylpiperidine N-Oxyl (TEMPO), Phthalimide N-Oxyl (PINO), and Related N-Oxyl Species: Electrochemical Properties and Their Use in Electrocatalytic Reactions

2018

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“…Furthermore, advances in mediated methods combined with the Shono‐type anodic oxidation: N‐ hydroxyphthalimide, [55] TEMPO, [56] aminoxyl mediators, [57] and electron‐proton transfer mediators [4] are unlocking new potential both for enhanced functional group compatibility, new multi‐component reactions, and allowing anodic oxidation to proceed at lower overpotentials than was previously possible. This will open new layers of reactivity that were previously out of reach.…”

Section: Discussionmentioning

confidence: 99%

Dialling‐In New Reactivity into the Shono‐Type Anodic Oxidation Reaction

Jones

2020

The Chemical Record

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This Personal Account describes the author's groups’ research in the field of electrosynthetic anodic oxidation, beginning with initial trial and error attempts with the Shono oxidation. Early setbacks with complex rotameric amide mixtures, provided the ideal environment for the discovery of the Oxa‐Shono reaction‐Osp2‐Csp3 bond cleavage of esters‐providing two useful products in one‐step: aldehyde selective oxidation level products and a mild de‐esterification method to afford carboxylic acids in the process. The development of the Oxa‐Shono reaction provided the impetus for the discovery of other electrically propelled‐Nsp2‐Csp2 and Nsp2‐Csp3‐bond breaking reactions in bioactive amide and sulfonamide systems. Understanding the voltammetric behaviour of the molecule under study, switching between controlled current‐ or controlled potential‐ electrolysis, and restricting electron flow (the reagent), affords exquisite control over the reaction outcomes in batch and flow. Importantly, this bio‐inspired advance in electrosynthetic dealkylation chemistry mimics the metabolic outcomes observed in nature.

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“…Furthermore, although the rate of cobalt dissolution appears to dominate in comparison to the other metals monitored by ICP-OES analysis, there are currently no insights into the role of a purely organic medium in the dissolution mechanism of such metals; thus, the reason for preferential solvation of cobalt is unknown. However, the kinetics and mechanism of cobalt dissolution have been studied extensively in acidic aqueous media and in the presence of organic additives [19][20][21]. Under such aqueous acidic conditions, the dissolution of cobalt and other transition metals proceeds via the interaction of metal oxide sites with H + ions and/or H − anion pairs with organic additives accelerating the process via complexing with the metal sites.…”

Section: Icp-oes Analysis Of Nmp Under Inert Operatingmentioning

confidence: 99%

Assessing the Oxidative Degradation of N-Methylpyrrolidone (NMP) in Microelectronic Fabrication Processes by Using a Multiplatform Analytical Approach

Lennon

Willox

Ramdas

et al. 2020

Journal of Analytical Methods in Chemistry

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During the construction of recording head devices, corrosion of metal features and subsequent deposition of corrosion by-products have been observed. Previous studies have determined that the use of N-methylpyrrolidone (NMP) may be a contributing factor. In this study, we report the use of a novel multiplatform analytical approach comprising of pH, liquid chromatography/UV detection (LC/UV), inductively coupled plasma optical emission spectroscopy (ICP-OES), and LC/mass spectrometry (LC/MS) to demonstrate that reaction conditions mimicking those of general photoresist removal processes can invoke the oxidation of NMP during the photolithography lift-off process. For the first time, we have confirmed that the oxidation of NMP lowers the pH, facilitating the dissolution of transition metals deposited on wafer substrates during post-mask and pre-lift-off processes in microelectronic fabrication. This negatively impacts upon the performance of the microelectronic device. Furthermore, it was shown that, by performing the process in an inert atmosphere, the oxidation of NMP was suppressed and the pH was stabilized, suggesting an affordable modification of the photolithography lift-off stage to enhance the quality of recording heads. This novel study has provided key data that may have a significant impact on current and future fabrication process design, optimization, and control. Results here suggest the inclusion of pH as a key process input variable (KPIV) during the design of new photoresist removal processes.

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Anodic oxidation of amides and lactams using N-hydroxyphthalimide as a mediator.

Cited by 37 publications

References 0 publications

Tetramethylpiperidine N-Oxyl (TEMPO), Phthalimide N-Oxyl (PINO), and Related N-Oxyl Species: Electrochemical Properties and Their Use in Electrocatalytic Reactions

Tetramethylpiperidine N-Oxyl (TEMPO), Phthalimide N-Oxyl (PINO), and Related N-Oxyl Species: Electrochemical Properties and Their Use in Electrocatalytic Reactions

Dialling‐In New Reactivity into the Shono‐Type Anodic Oxidation Reaction

Assessing the Oxidative Degradation of N-Methylpyrrolidone (NMP) in Microelectronic Fabrication Processes by Using a Multiplatform Analytical Approach

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