Iodine(III)‐Mediated Electrochemical Trifluoroethoxylactonisation: Rational Reaction Optimisation and Prediction of Mediator Activity

Möckel, Robert; Babaoglu, Emre; Hilt, Gerhard

doi:10.1002/chem.201804152

Cited by 47 publications

(23 citation statements)

References 49 publications

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“…Optimizations were done by a statistical approach also known as Design of Experiments (DoE) . The screenings investigated the concentrations of hydroxide C (NaOH) and iodide C (NaI) in the range from 1 m to 3 m and from 0.11 m to 0.55 m , respectively .…”

Section: Methodsmentioning

confidence: 99%

The “Green” Electrochemical Synthesis of Periodate

et al. 2020

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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.

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Section: Methodsmentioning

confidence: 99%

The “Green” Electrochemical Synthesis of Periodate

et al. 2020

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“…An increasingly popular mediatory system is represented by iodoarenes, which are anodically oxidized to the active aryl‐ λ 3 ‐iodane species . To date, the iodine(I)/iodine(III) couple has been used for anodic partial fluorination, C−N coupling between amides and arenes, trifluoroethoxylactonization, and enantioselective cyclizations (using a chiral iodoarene mediator) . In the course of our ongoing studies on sustainable electrolysis concepts, we have developed the bifunctional mediator salt 1a‐ClO 4 (see Figure ), which is composed of an iodophenyl unit and a trimethylammonium group, attached to each other via an alkylene linker .…”

Section: Introductionmentioning

confidence: 99%

Iodophenylsulfonates and Iodobenzoates as Redox‐Active Supporting Electrolytes for Electrosynthesis

et al. 2019

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Hypervalent iodine compounds constitute a popular class of reagents in organic chemistry. Regardless of whether they are generated in situ from an iodoarene precursor with a terminal oxidant or used in stoichiometric amounts, the resulting separation and waste issues are major challenges en route to sustainable and scalable processes. The electrochemical generation of iodine(III) compounds represents an attractive alternative, since electric current is used as traceless oxidant and unstable or hazardous species are conveniently generated in situ. In this context, we have explored the possibility for the use of iodoarene sulfonates and iodobenzoates as ex‐cell mediators for electrosynthesis in 1,1,1,3,3,3‐hexafluoroisopropanol. While 2‐, 3‐ and 4‐iodobenzoate salts proved to be impractical for various reasons, 2‐ and 4‐iodobenzenesulfonates salts can be selectively oxidized to the iodine(III) species and used for synthetic applications. The ionic tag on the mediator allows for electrolysis without supporting electrolyte additives and enables a straightforward recovery from the product mixture.

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“…Larger π systems also resulted in enhanced yields ( 21 , 37 %) (Scheme ). Recently, an electrochemical installation of TFE has been reported by an iodine(III)‐mediated cyclisation reaction for the synthesis of 4‐(2,2,2‐trifluoroethoxy)isochroman‐1‐ones …”

Section: Methodsmentioning

confidence: 99%

Electrochemical Synthesis of Fluorinated Orthoesters from 1,3‐Benzodioxoles

et al. 2019

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A scalable, dehydrogenative, and electrochemical synthesis of novel highly fluorinated orthoesters is reported. This protocol provides easy and direct access to a wide variety of derivatives, using a very simple electrolysis setup. These compounds are surprisingly robust towards base and acid with an unusual high lipophilicity, making them interesting motifs for potentially active compounds in medicinal chemistry or agro applications. The use of electricity enables a safe and environmentally benign chemical transformation as only electrons serve as oxidants.

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Iodine(III)‐Mediated Electrochemical Trifluoroethoxylactonisation: Rational Reaction Optimisation and Prediction of Mediator Activity

Cited by 47 publications

References 49 publications

The “Green” Electrochemical Synthesis of Periodate

The “Green” Electrochemical Synthesis of Periodate

Iodophenylsulfonates and Iodobenzoates as Redox‐Active Supporting Electrolytes for Electrosynthesis

Electrochemical Synthesis of Fluorinated Orthoesters from 1,3‐Benzodioxoles

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