Tailoring radicals by asymmetric electrochemical catalysis

Lin, Qifeng; Luo, Sanzhong

doi:10.1039/d0qo00803f

Cited by 23 publications

(12 citation statements)

References 26 publications

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“…The catalyst exchanges an electron with the substrate in an outer‐sphere or inner‐sphere manner to generate radical species (Figure 10A). The catalytic strategy not only allows the generation of the radical intermediates away from the electrode to reduce its local concentration but also at reduced electrode potential, providing better chemoselectivity and potentially stereoselectivity [74–75] . In addition, substrates that are difficult to undergo SET reactions on the electrode may participate in electrocatalytic reactions through hydrogen atom transfer (HAT) or inner‐sphere electron transfer [76–77] .…”

Section: Molecular Electrocatalysismentioning

confidence: 99%

Electrochemically Driven Radical Reactions: From Direct Electrolysis to Molecular Catalysis

Chen

2021

The Chemical Record

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Organic radicals are versatile synthetic intermediates that provide reactivities and selectivities complementary to ionic species. Despite its long history, electrochemically driven radical reactions remain limited in scope. In the past few years, there have been dramatic increase in research activity in organic electrochemistry. We have been developing electrochemical and electrophotocatalytic methods for the generation and synthetic utilization of organic radicals. In our studies, various radical species such as alkene and arene radical cations and carbon‐ and heteroatom‐centered radicals are generated from readily available precursors through direct electrolysis, molecular electrocatalysis or molecular electrophotocatalysis. These radical species undergo various inter‐ and intramolecular oxidative transformations to rapidly increase molecular complexity. The simultaneous occurrence of anodic oxidation and cathodic proton reduction allows the oxidative reactions to proceed through H2 evolution without external chemical oxidants.

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Section: Molecular Electrocatalysismentioning

confidence: 99%

Electrochemically Driven Radical Reactions: From Direct Electrolysis to Molecular Catalysis

Chen

2021

The Chemical Record

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“…The redox-triggered generation of highly reactive radical intermediates can enable powerful synthetic transformations while avoiding protecting groups. , The advantages provided by electrochemistry are of particular interest for the synthesis of active pharmaceutical ingredients (APIs), complex molecules requiring green and sustainable routes for their manufacturing on a large scale. However, the vast majority of electrosynthetic methods reported in the past decade ,, have focused on experiments carried out on the milligram scale, with only a handful of examples on >10 g scale. , In striving to achieve multikilogram-scale electrosynthesis for the APIs in our pipeline, we became interested in developing a clear workflow to guide the scale-up of electrochemical transformations. Beyond reaction optimization, we recognized the need to identify suitable equipment and key scaling parameters for translating a reaction from milligram to kilogram scale.…”

Section: Introductionmentioning

confidence: 99%

Kilo-Scale Electrochemical Oxidation of a Thioether to a Sulfone: A Workflow for Scaling up Electrosynthesis

Bottecchia

Lehnherr

Lévesque

et al. 2022

Org. Process Res. Dev.

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Organic electrosynthesis is a rapidly evolving field, providing powerful methods to assemble targets of interest in organic synthesis. Concerns around the scalability of electrochemical methods remain the biggest reason behind their scarce implementation in manufacturing routes for the pharmaceutical industry. To fill this gap, we report a workflow describing the key reaction parameters toward the successful scale-up of an organic electrosynthetic method from milligram to kilogram scale. The reaction used to demonstrate our workflow and scale-up in a flow setting was the oxidation of a thioether to its corresponding sulfone, a fragment of interest in an active pharmaceutical ingredient under development. The use of online flow nuclear magnetic resonance spectroscopy, offline ion chromatography, cyclic voltammetry, and density functional theory calculations provided insight into the reaction mechanism and side reactions.

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“…Recent developments in asymmetric electrochemical transformations have led to synthetic applications in the organic synthesis with good functional group tolerance and high enantioselectivity. 37 …”

Section: Discussionmentioning

confidence: 99%

“…Enantioselective electrochemical synthesis was envisioned for the synthesis of enantiomerically enriched, chiral compounds by electrochemical synthetic methods. 37 Organic electrosynthesis offers the possibility to perform reactions under exceedingly mild reaction conditions such as low temperatures, which are typically required to achieve highly enantioselective transformations. The existing methods of asymmetric electrochemical synthesis relied on the participation of an external source of chirality, such as chiral auxiliaries, chiral catalysts, chiral reagents, chiral electrodes, 116 chiral electrolytes, 117 or chiral solvents.…”

Section: Enantioselective Electrochemical Transformationsmentioning

confidence: 99%

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Organic Electrochemistry: Molecular Syntheses with Potential

et al. 2021

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Efficient and selective molecular syntheses are paramount to inter alia biomolecular chemistry and material sciences as well as for practitioners in chemical, agrochemical, and pharmaceutical industries. Organic electrosynthesis has undergone a considerable renaissance and has thus in recent years emerged as an increasingly viable platform for the sustainable molecular assembly. In stark contrast to early strategies by innate reactivity, electrochemistry was recently merged with modern concepts of organic synthesis, such as transition-metal-catalyzed transformations for inter alia C–H functionalization and asymmetric catalysis. Herein, we highlight the unique potential of organic electrosynthesis for sustainable synthesis and catalysis, showcasing key aspects of exceptional selectivities, the synergism with photocatalysis, or dual electrocatalysis, and novel mechanisms in metallaelectrocatalysis until February of 2021.

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Tailoring radicals by asymmetric electrochemical catalysis

Abstract: Asymmetric catalysis with radicals is challenging due to fleeting and neutral nature of radical species. We highlight herein asymmetric electrochemical catalysis as a powerful yet exquisite tool in facilitating chiral...

Cited by 23 publications

References 26 publications

Electrochemically Driven Radical Reactions: From Direct Electrolysis to Molecular Catalysis

Electrochemically Driven Radical Reactions: From Direct Electrolysis to Molecular Catalysis

Kilo-Scale Electrochemical Oxidation of a Thioether to a Sulfone: A Workflow for Scaling up Electrosynthesis

Organic Electrochemistry: Molecular Syntheses with Potential

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