Dehydrogenative Anodic Cyanation Reaction of Phenols in Benzylic Positions

Röckl, Johannes L.; Imada, Yasushi; Chiba, Kazuhiro; Franke, Robert; Waldvogel, Siegfried R.

doi:10.1002/celc.201801727

Cited by 18 publications

(10 citation statements)

References 53 publications

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“…The use of fluoroalcohols (in particular 1,1,1,3,3,3‐hexafluoropropan‐2‐ol, HFIP) in electrosynthesis has major advantages, as it modulates the reactivity of intermediates, and has an exceptional solvent microhetero‐geneity . This has been recently demonstrated by conversion of electrogenerated HFIP ethers with nucleophiles towards diarylmethanes and 2‐phenylacetonitriles . We have also developed efficient electrochemical C−N, S−S, C−C, and N−N coupling reactions involving phenols, anilides, and dianilides as substrates…”

Section: Methodsmentioning

confidence: 98%

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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Section: Methodsmentioning

confidence: 98%

Electrochemical Synthesis of Fluorinated Orthoesters from 1,3‐Benzodioxoles

et al. 2019

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“…As shown in previous work, the HFIP moiety can be used as a leaving group . We wanted to show that this strategy can also be applied to arenes and therefore various functionalization reactions were conducted (Scheme ).…”

Section: Methodsmentioning

confidence: 99%

“…In conclusion, we expanded the scope of the electroorganic synthesis of aryl HFIP ethers from our previous work to heterocycles. Key for these conversions is the amine‐HFIP electrolyte . In addition, the value of these intermediates was demonstrated in the activation within subsequent reactions.…”

Section: Methodsmentioning

confidence: 99%

Electrochemical C−H Functionalization of (Hetero)Arenes—Optimized by DoE

Dörr

Röckl

Rein

et al. 2020

Chemistry A European J

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A novel approach towards the activation of different arenes and purines including caffeine and theophylline is presented. The simple, safe and scalable electrochemical synthesis of 1,1,1,3,3,3‐hexafluoroisopropanol (HFIP) aryl ethers was conducted using an easy electrolysis setup with boron‐doped diamond (BDD) electrodes. Good yields up to 59 % were achieved. Triethylamine was used as a base as it forms a highly conductive media with HFIP, making additional supporting electrolytes superfluous. The synthesis was optimized using Design of Experiment (DoE) techniques giving a detailed insight to the significance of the reaction parameters. The mechanism was investigated by cyclic voltammetry (CV). Subsequent transition metal‐catalyzed as well as metal‐free functionalization led to interesting motifs in excellent yields up to 94 %.

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“…It was found that liberation of the benzylic cation is not necessary to achieve selective bond formation when stronger nucleophiles are used. [37] With cyanides, a direct substitution reaction is observed to yield 2-phenylacetonitriles, which represent important building blocks in organic synthesis. This structural feature is a precursor to many biologically active molecules such as 2phenylethylamines [45] or pharmaceuticals, such as the calcium ion channel blocker verapamil or the fungicide mandipropamid.…”

Section: Benzylic Anodic Cà H Functionalization With Hfip and Subsequmentioning

confidence: 99%

“…[35] Many more seminal applications of this powerful combination have been recently published and will be discussed within this review. [36][37][38][39][40]…”

Section: Introductionmentioning

confidence: 99%

Electrosynthesis 2.0 in 1,1,1,3,3,3‐Hexafluoroisopropanol/Amine Mixtures

2020

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The intention of this review is to highlight the innovative electrolyte combination of 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) with tertiary nitrogen bases in electro-organic synthesis. This easy applicable and promising mixture is not yet well established in electro-organic synthesis, but expands the various possibilities in the latter. Combinations of fluorinated alcohols with nitrogen bases form highly conductive electrolyte systems, which can be evaporated completely. Consequently, no additional supporting electrolyte is required and work-up procedures are tremendously simplified. With this electrolyte mixture carbon-carbon homo-and cross-coupling reactions of arenes and phenols have been established with substrates that have not been previously susceptible to the anodic dehydrogenative coupling reaction. The intermediate installation of highly fluorinated alkoxy moieties can be exploited for subsequent conversions as well as various benzylic functionalization, including asymmetric transformations. These transformations show unique selectivity and functional group tolerance making them highly applicable to the synthesis of sophisticated structural motifs, including natural products.

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Dehydrogenative Anodic Cyanation Reaction of Phenols in Benzylic Positions

Cited by 18 publications

References 53 publications

Electrochemical Synthesis of Fluorinated Orthoesters from 1,3‐Benzodioxoles

Electrochemical Synthesis of Fluorinated Orthoesters from 1,3‐Benzodioxoles

Electrochemical C−H Functionalization of (Hetero)Arenes—Optimized by DoE

Electrosynthesis 2.0 in 1,1,1,3,3,3‐Hexafluoroisopropanol/Amine Mixtures

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