Visible-Light-Induced Palladium-Catalyzed Generation of Aryl Radicals from Aryl Triflates

Maxim Ratushnyy; Nikita Kvasovs; Sumon Sarkar; Vladimir Gevorgyan

doi:10.1002/anie.201915962

Visible-Light-Induced Palladium-Catalyzed Generation of Aryl Radicals from Aryl Triflates

Maxim Ratushnyy, Nikita Kvasovs, Sumon Sarkar, Vladimir Gevorgyan

Research output: Contribution to journal › Article › peer-review

64 Scopus citations

Abstract

A mild visible-light-induced Pd-catalyzed intramolecular C−H arylation of amides is reported. The method operates by cleavage of a C(sp²)−O bond, leading to hybrid aryl Pd-radical intermediates. The following 1,5-hydrogen atom translocation, intramolecular cyclization, and rearomatization steps lead to valuable oxindole and isoindoline-1-one motifs. Notably, this method provides access to products with readily enolizable functional groups that are incompatible with traditional Pd-catalyzed conditions.

Original language	English (US)
Pages (from-to)	10316-10320
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	59
Issue number	26
DOIs	https://doi.org/10.1002/anie.201915962
State	Published - Jun 22 2020

Keywords

homolysis
light-mediated reactions
palladium
radicals
triflates

ASJC Scopus subject areas

Catalysis
Chemistry(all)

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10.1002/anie.201915962

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title = "Visible-Light-Induced Palladium-Catalyzed Generation of Aryl Radicals from Aryl Triflates",

abstract = "A mild visible-light-induced Pd-catalyzed intramolecular C−H arylation of amides is reported. The method operates by cleavage of a C(sp2)−O bond, leading to hybrid aryl Pd-radical intermediates. The following 1,5-hydrogen atom translocation, intramolecular cyclization, and rearomatization steps lead to valuable oxindole and isoindoline-1-one motifs. Notably, this method provides access to products with readily enolizable functional groups that are incompatible with traditional Pd-catalyzed conditions.",

keywords = "homolysis, light-mediated reactions, palladium, radicals, triflates",

author = "Maxim Ratushnyy and Nikita Kvasovs and Sumon Sarkar and Vladimir Gevorgyan",

note = "Funding Information: This research was supported by the National Institutes of Health (GM120281), National Science Foundation (CHE‐1936422), and Welch Foundation (Chair, AT‐0041). We thank Prof. Anvar Zakhidov (UTD) and Dr. Alexios Paradimitratos (UTD) for the help with EPR experiments. Publisher Copyright: {\textcopyright} 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

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month = jun,

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doi = "10.1002/anie.201915962",

language = "English (US)",

volume = "59",

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AU - Ratushnyy, Maxim

AU - Kvasovs, Nikita

AU - Sarkar, Sumon

AU - Gevorgyan, Vladimir

N1 - Funding Information: This research was supported by the National Institutes of Health (GM120281), National Science Foundation (CHE‐1936422), and Welch Foundation (Chair, AT‐0041). We thank Prof. Anvar Zakhidov (UTD) and Dr. Alexios Paradimitratos (UTD) for the help with EPR experiments. Publisher Copyright: © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2020/6/22

Y1 - 2020/6/22

N2 - A mild visible-light-induced Pd-catalyzed intramolecular C−H arylation of amides is reported. The method operates by cleavage of a C(sp2)−O bond, leading to hybrid aryl Pd-radical intermediates. The following 1,5-hydrogen atom translocation, intramolecular cyclization, and rearomatization steps lead to valuable oxindole and isoindoline-1-one motifs. Notably, this method provides access to products with readily enolizable functional groups that are incompatible with traditional Pd-catalyzed conditions.

AB - A mild visible-light-induced Pd-catalyzed intramolecular C−H arylation of amides is reported. The method operates by cleavage of a C(sp2)−O bond, leading to hybrid aryl Pd-radical intermediates. The following 1,5-hydrogen atom translocation, intramolecular cyclization, and rearomatization steps lead to valuable oxindole and isoindoline-1-one motifs. Notably, this method provides access to products with readily enolizable functional groups that are incompatible with traditional Pd-catalyzed conditions.

KW - homolysis

KW - light-mediated reactions

KW - palladium

KW - radicals

KW - triflates

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JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

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ER -

Visible-Light-Induced Palladium-Catalyzed Generation of Aryl Radicals from Aryl Triflates

Abstract

Keywords

ASJC Scopus subject areas

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