The “Green” Electrochemical Synthesis of Periodate

Abstract

High‐grade periodate is relatively expensive, but is required for many sensitive applications such as the synthesis of active pharmaceutical ingredients. These high costs originate from using lead dioxide anodes in contemporary electrochemical methods and from expensive starting materials. A direct and cost‐efficient electrochemical synthesis of periodate from iodide, which is less costly and relies on a readily available starting material, is reported. The oxidation is conducted at boron‐doped diamond anodes, which are durable, metal‐free, and nontoxic. The avoidance of lead dioxide ultimately lowers the cost of purification and quality assurance. The electrolytic process was optimized by statistical methods and was scaled up in an electrolysis flow cell that enhanced the space–time yields by a cyclization protocol. An LC‐PDA analytical protocol was established enabling simple quantification of iodide, iodate, and periodate simultaneously with remarkable precision.

Electrosynthetic Screening and Modern Optimization Strategies for Electrosynthesis of Highly Value‐added Products

“…[14,35] Furthermore, our group used a DoE supported optimization for the electrochemical oxidation of sodium iodide to periodate at a BDD anode. [36] Previous methods of producing periodate are based on the use of lead dioxide anodes, but they are known to slowly decompose into solution during oxidation. Therefore, expensive purification of periodate is necessary before use as reagent for sensitive applications.…”

Anodische dehydrierende Cyaniminierung von Thioethern: eine einfache und nachhaltige Synthese von N‐Cyansulfiliminen

“…Es sind einige Synthesen in der Literatur zum Aufbau von Sulfoximinen ausgehend von Sulfiliminen unter der Verwendung von Oxidationsmitteln wie KMnO 4 [30] oder NaIO 4 [31] beschrieben. Daher waren wir interessiert, ob die Oxidation mit dem kürzlich von uns beschriebenen elektrochemisch generierten Na 3 H 2 IO 6 ebenfalls möglich ist [32] . Dieses Periodat ist aus einfachsten Iodquellen zugänglich und kann in der Synthese pharmazeutisch relevanter Verbindungen eingesetzt und rückgewonnen werden [33] …”

Unexpected selective alkaline periodate oxidation of chitin for the isolation of chitin nanocrystals

“…Periodate can selectively cleave the carbon-carbon bonds of a variety of 1,2-difunctionalised alkanes and introduce aldehyde groups, 1 which makes it an increasingly viable tool in carbohydrate chemistry for promising applications. [2][3][4][5][6] Despite the tremendous progress made in the utilization of chitin over the past decades, periodate oxidation remained absent from the toolbox for the direct modification of chitin. This is primarily due to the fact that the N-acetylation of the amino groups prevents the cleavage of C-C bonds between C2 and C3 by metaperiodate oxidation.…”

“…26 However, due to the financial risks associated with ChNC production, 27 ChNCs have not been widely used. Thus, with the selectivity of alkaline periodate oxidation and the characteristic that periodate can be cost-efficiently regenerated from iodate under alkaline conditions, 6,17,28 it should be very attractive in the production of ChNCs via alkaline periodate oxidation from the massive amount of bio-waste accumulated by marine-capture fisheries, food industry or other resources (up to 10 gigatons chitin per year). 27 In the present work, we show the unexplored periodate oxidation on chitin in alkaline media, which selectively attacks the non-ordered domains of chitin in a one-pot process through a starting weak deacetylation and subsequent efficient oxidation of deacetylated glucosamine units of low quantities.…”

“…Besides, Waldvogel's group recently reported the direct and cost-efficient electrochemical synthesis of periodate from iodide and iodate on a large scale, which is less costly and relies on a readily available starting material, such as I − or IO 3 − . 6 Based on this well-developed electrochemical technology, a feasible protocol can be suggested to deal with the potential environmental issues and high cost of periodate oxidants. The solution containing the periodate and iodate after the isolation of ChNCs can be separated from the solid part and reused for the regeneration of periodate via the electrochemical oxidation.…”