Transition Metal-Catalyzed Selective Carbon–Carbon Bond Cleavage of Vinylcyclopropanes in Cycloaddition Reactions

Chemical Reviews, Journal Year: 2020, Volume and Issue: 121(1), P. 110 - 139

Published: Aug. 6, 2020

In this review, transition metal-catalyzed methodologies and applications that exploit C–C bond cleavage of vinylcyclopropanes (VCPs) are summarized with a focus on cycloaddition related addition reactions. Transition metals, including palladium, nickel, iron, ruthenium, rhodium, cobalt, iridium, can catalyze the bonds in activated or nonactivated VCPs. Additionally, these bond-breaking reactions occur as intra- intermolecular processes. The properties VCPs discussed Introduction. Various involving then next chapter. cycloadditions following Finally, challenges potential opportunities outlined last

Language: Английский

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Electrophotocatalytic Decarboxylative C−H Functionalization of Heteroarenes

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(26), P. 10626 - 10632

Published: March 30, 2020

Abstract Decarboxylative C−H functionalization reactions are highly attractive methods for forging carbon–carbon bonds considering their inherent step‐ and atom‐economical features the pervasiveness of carboxylic acids bonds. An ideal approach to achieve these dehydrogenative transformations is through hydrogen evolution without using any chemical oxidants. However, effective couplings by decarboxylative bond formation with proton reduction remain an unsolved challenge. Herein, we report electrophotocatalytic that merges organic electrochemistry photocatalysis efficient direct alkylation carbamoylation heteroaromatic compounds evolution. This method, which combines high efficiency selectivity in promoting decarboxylation superiority effecting reduction, enables coupling a wide range bases variety oxamic acids. Advantageously, this method scalable decagram amounts, applicable late‐stage drug molecules.

Language: Английский

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Electrochemically Enabled, Nickel-Catalyzed Dehydroxylative Cross-Coupling of Alcohols with Aryl Halides

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(9), P. 3536 - 3543

Published: Feb. 23, 2021

As alcohols are ubiquitous throughout chemical science, this functional group represents a highly attractive starting material for forging new C–C bonds. Here, we demonstrate that the combination of anodic preparation alkoxy triphenylphosphonium ion and nickel-catalyzed cathodic reductive cross-coupling provides an efficient method to construct C(sp2)–C(sp3) bonds, in which free aryl bromides—both readily available chemicals—can be directly used as coupling partners. This paired electrolysis reaction features broad substrate scope bearing wide gamut functionalities, was illustrated by late-stage arylation several structurally complex natural products pharmaceuticals.

Language: Английский

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Asymmetric Electrochemical Transformations

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(31), P. 12612 - 12622

Published: Feb. 14, 2020

Abstract The field of electrochemical synthesis has developed rapidly over the last decade and provided alternative synthetic methods with absence stoichiometric amounts chemical oxidants or reductants. Although sustainable electrosynthetic procedures have been developed, relatively few examples highly enantioselective catalytic electrosynthesis reported to date. development general strategies for enantiocontrol thus proven be a considerable challenge. This Minireview highlights current knowledge recent advances in utility transformations asymmetric synthesis. Specifically, three major types strategy are outlined, including activation chiral catalyst‐bound substrates, cascade processes, chemically modified electrodes.

Language: Английский

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Cross-dehydrogenative coupling: a sustainable reaction for C–C bond formations

Green Chemistry, Journal Year: 2021, Volume and Issue: 23(18), P. 6789 - 6862

Published: Jan. 1, 2021

We provide a review of the progress cross-dehydrogenative coupling reactions in constructing wide variety C–C bonds. Sustainable can be combined with multiple forms energy output.

Language: Английский

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Nickel‐Catalyzed Electrochemical Reductive Relay Cross‐Coupling of Alkyl Halides to Aryl Halides

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(16), P. 6520 - 6524

Published: Dec. 3, 2019

A highly regioselective Ni-catalyzed electrochemical reductive relay cross-coupling between an aryl halide and alkyl has been developed in undivided cell. Various functional groups are tolerated under these mild reaction conditions, which provides alternative approach for the synthesis of 1,1-diarylalkanes.

Language: Английский

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Organic Electrosynthesis: Applications in Complex Molecule Synthesis

ChemElectroChem, Journal Year: 2019, Volume and Issue: 6(16), P. 4067 - 4092

Published: May 23, 2019

Abstract Organic electrosynthesis is an enabling and sustainable technology, which constitutes a rapidly expanding field of research. Electrochemical approaches serve as convenient green alternatives to stoichiometric toxic chemical redox agents. Electrosynthesis promising platform for harnessing the unique reactivity profiles radical intermediates, expediting development new reaction manifolds. This Review highlights both anodic cathodic methods construction various kinds complex molecules.

Language: Английский

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Enantioselective Ni-Catalyzed Electrochemical Synthesis of Biaryl Atropisomers

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(22), P. 9872 - 9878

Published: May 11, 2020

A scalable enantioselective nickel-catalyzed electrochemical reductive homocoupling of aryl bromides has been developed, affording enantioenriched axially chiral biaryls in good yield under mild conditions using electricity as a reductant an undivided cell. Common metal reductants such Mn or Zn powder resulted significantly lower yields the absence electric current otherwise identical conditions, underscoring enhanced reactivity provided by combination transition catalysis and electrochemistry.

Language: Английский

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Nickel‐Catalyzed Thiolation of Aryl Halides and Heteroaryl Halides through Electrochemistry

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(15), P. 5033 - 5037

Published: Feb. 8, 2019

Transition-metal-catalyzed coupling reactions are useful tools for synthesizing aryl sulfur compounds. However, conventional transition-metal-catalyzed thiolation of bromides and chlorides typically requires the use strong base under elevated reaction temperature. Herein, we report first examples nickel-catalyzed electrochemical in absence an external at room temperature using undivided cells.

Language: Английский

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Reproducibility in Electroorganic Synthesis—Myths and Misunderstandings

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(27), P. 14750 - 14759

Published: Jan. 15, 2021

The use of electric current as a traceless activator and reagent is experiencing renaissance. This sustainable synthetic method evolving into hot topic in contemporary organic chemistry. Since researchers with various scientific backgrounds are entering this interdisciplinary field, different parameters methods reported to describe the experiments. variation can lead problems reproducibility electroorganic syntheses. As an example, such density or electrode distance some cases more significant than often anticipated. Minireview provides guidelines on reporting electrosynthetic data dispels myths about technique, thereby streamlining experimental facilitate reproducibility.

Language: Английский

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