Accelerating sulfonyl fluoride synthesis through electrochemical oxidative coupling of thiols and potassium fluoride in flow

Cao, Yiran; Adriaenssens, Benjamin; Bartolomeu, Aloísio de Andrade; Laudadio, Gabriele; Oliveira, Kléber T. de; Noël, Timothy

doi:10.1007/s41981-019-00070-9

Cited by 35 publications

(18 citation statements)

References 30 publications

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“…After the electrochemical step, phenyl sulfonyl fluoride was combined with a stream containing phenol, which enables the SuFEx chemistry in flow and yields the corresponding phenyl sulfonate derivative. 36 This strategy enables to produce volatile sulfonyl fluorides and immediately utilize these moieties without intermediate isolation.…”

Section: Combine It All—multistep Reaction Sequences In Flowmentioning

confidence: 99%

The Fundamentals Behind the Use of Flow Reactors in Electrochemistry

2019

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ConspectusIn the past decade, research into continuous-flow chemistry has gained a lot of traction among researchers in both academia and industry. Especially, microreactors have received a plethora of attention due to the increased mass and heat transfer characteristics, the possibility to increase process safety, and the potential to implement automation protocols and process analytical technology. Taking advantage of these aspects, chemists and chemical engineers have capitalized on expanding the chemical space available to synthetic organic chemists using this technology.Electrochemistry has recently witnessed a renaissance in research interests as it provides chemists unique and tunable synthetic opportunities to carry out redox chemistry using electrons as traceless reagents, thus effectively avoiding the use of hazardous and toxic reductants and oxidants. The popularity of electrochemistry stems also from the potential to harvest sustainable electricity, derived from solar and wind energy. Hence, the electrification of the chemical industry offers an opportunity to locally produce commodity chemicals, effectively reducing inefficiencies with regard to transportation and storage of hazardous chemicals.The combination of flow technology and electrochemistry provides practitioners with great control over the reaction conditions, effectively improving the reproducibility of electrochemistry. However, carrying out electrochemical reactions in flow is more complicated than just pumping the chemicals through a narrow-gap electrolytic cell. Understanding the engineering principles behind the observations can help researchers to exploit the full potential of the technology. Thus, the prime objective of this Account is to provide readers with an overview of the underlying engineering aspects which are associated with continuous-flow electrochemistry. This includes a discussion of relevant mass and heat transport phenomena encountered in electrochemical flow reactors. Next, we discuss the possibility to integrate several reaction steps in a single streamlined process and the potential to carry out challenging multiphase electrochemical transformations in flow. Due to the high control over mass and heat transfer, electrochemical reactions can be carried out with great precision and reproducibility which provide opportunities to enhance and tune the reaction selectivity. Finally, we detail on the scale-up potential of flow electrochemistry and the importance of small interelectrode gaps on pilot and industrial-scale electrochemical processes. Each principle has been illustrated with a relevant organic synthetic example. In general, we have aimed to describe the underlying engineering principles in simple words and with a minimum of equations to attract and engage readers from both a synthetic organic chemistry and a chemical engineering background. Hence, we anticipate that this Account will serve as a useful guide through the fascinating world of flow electrochemistry.

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Section: Combine It All—multistep Reaction Sequences In Flowmentioning

confidence: 99%

The Fundamentals Behind the Use of Flow Reactors in Electrochemistry

2019

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“…32 In particular, electrochemical methods have been demonstrated to be capable of incorporating either sulfur 33,34 or fluorine [35][36][37][38] functionalities into diverse organic frameworks. Inspired by the elegant sulfonyl fluoride (RSO2-F) synthesis via the electrochemical oxidative coupling of thiols (RSH) and potassium fluoride (KF) reported by Noël and co-workers, 39,40 we speculated that electrochemistry should be an ideal solution to simultaneously 41 introduce both fluorine and sulfur in a controllable oxidation state into alkenes. Herein, we report an electrochemical radical-polar crossover approach for the highly selective fluorosulfenylation and fluorosulfoxidation of alkenes in which the selectivity was well controlled by the judicious choice of the applied potential (Scheme 1D).…”

Section: Scheme | Direct Incorporation Of Sulfur and Fluorine Elements Into Alkenesmentioning

confidence: 99%

Electrochemistry Enabled Selective Vicinal Fluorosulfenylation and Fluorosulfoxidation of Alkenes

Jiang

et al. 2021

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Both sulfur and fluorine play important roles in organic synthesis, the life science, and materials science. The direct incorporation of these elements into organic scaffolds with precise control of the oxidation states of sulfur moieties is of great significance. Herein, we report the highly selective electrochemical vicinal fluorosulfenylation and fluorosulfoxidation reactions of alkenes, which were enabled by the unique ability of electrochemistry to dial in the potentials on demand. Preliminary mechanistic investigations revealed that the fluorosulfenylation reaction proceeded through a radical-polar crossover mechanism involving a key episulfonium ion intermediate. Subsequent electrochemical oxidation of fluorosulfides to fluorosulfoxides were readily achieved under a higher applied potential with the adventitious H2O in the reaction mixture.

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“…Based on these results (Figure 2), we decided to use our flow cell in a constant‐potential or potentiostatic operation mode and set the cell potential at either 2.4 or 2.9 V (Table 1; see also the Supporting Information). In our experience, a potentiostatic mode in combination with a continuous‐flow operation allows to obtain high selectivities for a targeted compound without the need to extend the reaction times [29,37,38] . Extended reaction times, observed with potentiostatic electrochemical transformations, is an often encountered problem in batch electrolysis as the current decreases with increasing conversions [39] .…”

Section: Figurementioning

confidence: 99%

“…In our experience, a potentiostatic mode in combination with a continuous-flow operation allows to obtain high selectivities for a targeted compound without the need to extend the reaction times. [29,37,38] Extended reaction times, observed with potentiostatic electrochemical transformations, is an often encountered problem in batch electrolysis as the current decreases with increasing conversions. [39] However, in flow, high substrate concentrations are encountered at the entrance of the reactor and low concentrations at the exit, leading to an average current density over the entire reactor length.…”

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confidence: 99%

A Divergent Paired Electrochemical Process for the Conversion of Furfural Using a Divided‐Cell Flow Microreactor

et al. 2020

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Furfural is a prominent, non‐petroleum‐based chemical feedstock material, derived from abundantly available hemicellulose. Hence, its derivatization into other useful biobased chemicals is a subject of high interest in contemporary academic and industrial research activities. While most strategies to convert furfural require energy‐intensive reaction routes, the use of electrochemical activation allows to provide a sustainable and green alternative. Herein, a disparate approach for the conversion of furfural is reported based on a divergent paired electrochemical conversion, enabling the simultaneous production of 2(5 H )‐furanone via an anodic oxidation, and the generation of furfuryl alcohol and/or hydrofuroin via a cathodic reduction. Using water as solvent and NaBr as supporting electrolyte and electron‐mediator, a green and sustainable process was developed, which maximizes productive use of electricity and minimizes byproduct formation.

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Accelerating sulfonyl fluoride synthesis through electrochemical oxidative coupling of thiols and potassium fluoride in flow

Cited by 35 publications

References 30 publications

The Fundamentals Behind the Use of Flow Reactors in Electrochemistry

The Fundamentals Behind the Use of Flow Reactors in Electrochemistry

Electrochemistry Enabled Selective Vicinal Fluorosulfenylation and Fluorosulfoxidation of Alkenes

A Divergent Paired Electrochemical Process for the Conversion of Furfural Using a Divided‐Cell Flow Microreactor

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