Anodic Dehydrogenative Cyanamidation of Thioethers: Simple and Sustainable Synthesis of <i>N</i>‐Cyanosulfilimines

Klein, Martin; Waldvogel, Siegfried R.

doi:10.1002/anie.202109033

Cited by 20 publications

(14 citation statements)

References 55 publications

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“…The combination of MeCN with low amounts of MeOH to generate a base leads to desirable yields. [33] Another promising tool for a controlled proton concentration in the dehydrogenative coupling is the combination of HFIP and an amine base. This combination has been shown to be successful, since HFIP acts as a proton source, but its acidity is tamed by the amine base to readily generate a conductive solution.…”

Section: Protic Electrolytesmentioning

confidence: 99%

Counter Electrode Reactions—Important Stumbling Blocks on the Way to a Working Electro‐organic Synthesis

Klein

Waldvogel

2022

Angew Chem Int Ed

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Over the past two decades, electro‐organic synthesis has gained significant interest, both in technical and academic research as well as in terms of applications. The omission of stoichiometric oxidizers or reducing agents enables a more sustainable route for redox reactions in organic chemistry. Even if it is well‐known that every electrochemical oxidation is only viable with an associated reduction reaction and vice versa, the relevance of the counter reaction is often less addressed. In this Review, the importance of the corresponding counter reaction in electro‐organic synthesis is highlighted and how it can affect the performance and selectivity of the electrolytic conversion. A selection of common strategies and unique concepts to tackle this issue are surveyed to provide a guide to select appropriate counter reactions for electro‐organic synthesis.

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Section: Protic Electrolytesmentioning

confidence: 99%

Counter Electrode Reactions—Important Stumbling Blocks on the Way to a Working Electro‐organic Synthesis

Klein

Waldvogel

2022

Angew Chem Int Ed

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“…The electrochemically produced para-periodate has been successfully demonstrated to efficiently degrade lignin, [56] and to achieve the final oxidative step in the synthesis of levetiracetam and sulfoximines. [57,58] Here, we demonstrate that electrolyses to the periodate platform oxidizer are highly robust against the presence of several organic contaminants (i.e., dyes, APIs, and other iodine compounds). Mineralization of these impurities is not harming the oxidative recycling of periodate.…”

Section: Introductionmentioning

confidence: 75%

“…Highly toxic anti‐reducing agents could be omitted using a divided cell setup employing a Nafion membrane. The electrochemically produced para ‐periodate has been successfully demonstrated to efficiently degrade lignin, [56] and to achieve the final oxidative step in the synthesis of levetiracetam and sulfoximines [57,58] …”

Section: Introductionmentioning

confidence: 99%

Robust and Self‐Cleaning Electrochemical Production of Periodate

et al. 2022

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Periodate, a platform oxidizer, can be electrochemically recycled in a self-cleaning process. Electrosynthesis of periodate is well established at boron-doped diamond (BDD) anodes. However, recovered iodate and other iodo species for recycling can contain traces of organic impurities from previous applications. For the first time, it was shown that the organic impurities do not hamper the electrochemical re-oxidation of used periodate. In a hydroxyl-mediated environment, the organic compounds form CO 2 and H 2 O during the degradation process. This process is often referred to as "cold combustion" and provides orthogonal conditions to periodate synthesis. To demonstrate the strategy, different dyes, pharmaceutically active ingredients, and iodine compounds were added as model contaminations into the process of electrochemical periodate production. UV/ Vis spectroscopy, NMR spectroscopy, and mass spectrometry (MS) were used to monitor the degradation of organic molecules, and liquid chromatography-MS was used to control the purity of periodate. As a representative example, dimethyl 5-iodoisophthalate (2 mm), was degraded in 90, 95, and 99 % while generating 0.042, 0.054, and 0.082 kilo equiv. of periodate, respectively. In addition, various organic iodo compounds could be fed into the periodate generation for upcycling such iodocontaining waste, for example, contrast media.

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“…Finally, we want to focus on biologically active N -cyanosulfoximines, which represent a hot topic currently. − Very recently, an electrochemical method was developed by our group and the efficient synthesis of sulfoxaflor ( Isoclast ), a commercial insecticide, was showcased (Scheme ). The two-step sequence followed an electrochemical oxidation to the N -cyanosulfilimine and a ruthenium-catalyzed oxidation with periodate to the corresponding sulfoximine, whereby electrochemically produced periodate was used.…”

Section: Transition-metal-catalyzed Oxidations With Periodatementioning

confidence: 99%

Synthesis and Applications of Periodate for Fine Chemicals and Important Pharmaceuticals

Arndt

Kohlpaintner

Donsbach

et al. 2022

Org. Process Res. Dev.

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An emerging interest for the application of periodate in the synthesis of active pharmaceutical ingredients (APIs) and for the valorization of renewable feedstock is eminent. However, periodate exhibits a high molecular mass, is expensive compared to other common bulk-oxidizers and is used only reluctantly in technical applications. Recently, a new and green electrochemical synthesis was established. The preparation and regeneration method for periodate lowers costs and enables the use of periodate in the synthesis of regulated products. This review will briefly introduce the key innovations in the electrochemical synthesis of periodate and will survey the most important applications of periodate in the production of fine chemicals.

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Anodic Dehydrogenative Cyanamidation of Thioethers: Simple and Sustainable Synthesis of N‐Cyanosulfilimines

Cited by 20 publications

References 55 publications

Counter Electrode Reactions—Important Stumbling Blocks on the Way to a Working Electro‐organic Synthesis

Counter Electrode Reactions—Important Stumbling Blocks on the Way to a Working Electro‐organic Synthesis

Robust and Self‐Cleaning Electrochemical Production of Periodate

Synthesis and Applications of Periodate for Fine Chemicals and Important Pharmaceuticals

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