Friedel–Crafts-Type Reactions with Electrochemically Generated Electrophiles from Donor–Acceptor Cyclopropanes and -Butanes

Kolb, Simon; Ahlburg, Nils L.; Werz, Daniel B.

doi:10.1021/acs.orglett.1c01890

Cited by 45 publications

(13 citation statements)

References 61 publications

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“…However, there are several challenges for such a transformation. For example, the electrochemical ring-opening difunctionalization of CC single bond was limited to oxidative process of donor–acceptor cyclopropanes by anodic oxidation. , Moreover, the cyclopropanes, such as 1,2-diphenylcyclopropane, has LUMO energy within 0.2 eV of that of benzene (E 0 = −3.42 V vs SCE), which means it might be as difficult to be reduced as benzene. In addition, many side reactions, such as hydrocarboxylation and reduction, might occur to result in low selectivity.…”

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confidence: 99%

Electrochemical Ring-Opening Dicarboxylation of Strained Carbon–Carbon Single Bonds with CO₂: Facile Synthesis of Diacids and Derivatization into Polyesters

et al. 2022

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Diacids are important monomers in the polymer industry to construct valuable materials. Dicarboxylation of unsaturated bonds, such as alkenes and alkynes, with CO2 has been demonstrated as a promising synthetic method. However, dicarboxylation of CC single bonds with CO2 has rarely been investigated. Herein we report a novel electrochemical ring-opening dicarboxylation of CC single bonds in strained rings with CO2. Structurally diverse glutaric acid and adipic acid derivatives were synthesized from substituted cyclopropanes and cyclobutanes in moderate to high yields. In contrast to oxidative ring openings, this is also the first realization of an electroreductive ring-opening reaction of strained rings, including commercialized ones. Control experiments suggested that radical anions and carbanions might be the key intermediates in this reaction. Moreover, this process features high step and atom economy, mild reaction conditions (1 atm, room temperature), good chemoselectivity and functional group tolerance, low electrolyte concentration, and easy derivatization of the products. Furthermore, we conducted polymerization of the corresponding diesters with diols to obtain a potential UV-shielding material with a self-healing function and a fluorine-containing polyester, whose performance tests showed promising applications.

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confidence: 99%

Electrochemical Ring-Opening Dicarboxylation of Strained Carbon–Carbon Single Bonds with CO₂: Facile Synthesis of Diacids and Derivatization into Polyesters

et al. 2022

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“…Various valuable dicarboxylic acids were achieved efficiently by electroreduction of cyclopropanes and cyclobutanes with CO 2 . Moreover, different from electro-oxidative ring-opening difunctionalization, which are limited to the anodic oxidative radical cations’ intermediates [ 64 , 65 , 66 ]. The author first realized an electro-reductive ring-opening strategy, one which involved the key radical anions and carbanions intermediates.…”

Section: Electrochemical Reductionmentioning

confidence: 99%

Electroreductively Induced Radicals for Organic Synthesis

Xiang

He²,

Qian³

et al. 2023

Molecules

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Organic electrochemistry has attracted tremendous interest within the novel sustainable methodologies that have not only reduced the undesired byproducts, but also utilized cleaner and renewable energy sources. Particularly, oxidative electrochemistry has gained major attention. On the contrary, reductive electrolysis remains an underexplored research direction. In this context, we discuss advances in transition-metal-free cathodically generated radicals for selective organic transformations since 2016. We highlight the electroreductive reaction of alkyl radicals, aryl radicals, acyl radicals, silyl radicals, fluorosulfonyl radicals and trifluoromethoxyl radicals.

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“…Great success of the donor-acceptor cyclopropane concept in organic synthesis stimulated a renaissance of interest to electrochemical ring opening. Quite recently, two publications from the Werz group appeared concerning anodic activation of donor-acceptor cyclopropanes followed by their functionalization with arenes [43] or yielding oxy-ketones or 1,2-dioxanes [44]; the latter process was inspired by a previous report of Buriez [45]. The anodic fluorination of arylcyclopropane derivatives was reported recently [46,47], difluorinated or oxyfluorinated products were obtained [47].…”

Section: Introductionmentioning

confidence: 99%

Reductive opening of a cyclopropane ring in the Ni(II) coordination environment: a route to functionalized dehydroalanine and cysteine derivatives

Levitskiy¹,

Aglamazova²,

Grishin³

et al. 2022

Beilstein J. Org. Chem.

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The involvement of an α,α-cyclopropanated amino acid in the chiral Ni(II) coordination environment in the form of a Schiff base is considered as a route to electrochemical broadening of the donor–acceptor cyclopropane concept in combination with chirality induction in the targeted products. A tendency to the reductive ring-opening and the follow-up reaction paths of thus formed radical anions influenced by substituents in the cyclopropane ring are discussed. Optimization of the reaction conditions opens a route to the non-proteinogenic amino acid derivatives containing an α–β or β–γ double C=C bond in the side chain; the regioselectivity can be tuned by the addition of Lewis acids. One-pot combination of the reductive ring opening and subsequent addition of thiols allows obtaining the cysteine derivatives in practical yields and with high stereoselectivity at the removed β-stereocenter.

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Friedel–Crafts-Type Reactions with Electrochemically Generated Electrophiles from Donor–Acceptor Cyclopropanes and -Butanes

Cited by 45 publications

References 61 publications

Electrochemical Ring-Opening Dicarboxylation of Strained Carbon–Carbon Single Bonds with CO₂: Facile Synthesis of Diacids and Derivatization into Polyesters

Electrochemical Ring-Opening Dicarboxylation of Strained Carbon–Carbon Single Bonds with CO₂: Facile Synthesis of Diacids and Derivatization into Polyesters

Electroreductively Induced Radicals for Organic Synthesis

Reductive opening of a cyclopropane ring in the Ni(II) coordination environment: a route to functionalized dehydroalanine and cysteine derivatives

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Friedel–Crafts-Type Reactions with Electrochemically Generated Electrophiles from Donor–Acceptor Cyclopropanes and -Butanes

Cited by 45 publications

References 61 publications

Electrochemical Ring-Opening Dicarboxylation of Strained Carbon–Carbon Single Bonds with CO2: Facile Synthesis of Diacids and Derivatization into Polyesters

Electrochemical Ring-Opening Dicarboxylation of Strained Carbon–Carbon Single Bonds with CO2: Facile Synthesis of Diacids and Derivatization into Polyesters

Electroreductively Induced Radicals for Organic Synthesis

Reductive opening of a cyclopropane ring in the Ni(II) coordination environment: a route to functionalized dehydroalanine and cysteine derivatives

Contact Info

Product

Resources

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Electrochemical Ring-Opening Dicarboxylation of Strained Carbon–Carbon Single Bonds with CO₂: Facile Synthesis of Diacids and Derivatization into Polyesters

Electrochemical Ring-Opening Dicarboxylation of Strained Carbon–Carbon Single Bonds with CO₂: Facile Synthesis of Diacids and Derivatization into Polyesters