Redox Inversion: A Radical Analogue of Umpolung Reactivity for Base- and Metal-Free Catalytic C(sp3)-C(sp3) Coupling

Chris M. Seong; Annabel Q. Ansel; Courtney C. Roberts

doi:10.1021/acs.joc.2c02877

Redox Inversion: A Radical Analogue of Umpolung Reactivity for Base- and Metal-Free Catalytic C(sp³)-C(sp³) Coupling

Chris M. Seong, Annabel Q. Ansel, Courtney C. Roberts

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

9 Scopus citations

Abstract

The construction of alkyl-alkyl bonds is a powerful tool in organic synthesis. Redox inversion, defined as switching the donor/acceptor profile of a functional group to its acceptor/donor profile, is used for C(sp³)-C(sp³) coupling. We report a photocatalytic coupling of carboxylic acids to form bibenzyls through a radical-radical coupling. Mechanistic insight is gained through control reactions. This unexplored redox-opposite relationship between a carboxylic acid and its redox-active ester is implemented in catalysis.

Original language	English (US)
Pages (from-to)	3935-3940
Number of pages	6
Journal	Journal of Organic Chemistry
Volume	88
Issue number	6
DOIs	https://doi.org/10.1021/acs.joc.2c02877
State	Published - Mar 17 2023
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2023 American Chemical Society

PubMed: MeSH publication types

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10.1021/acs.joc.2c02877

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title = "Redox Inversion: A Radical Analogue of Umpolung Reactivity for Base- and Metal-Free Catalytic C(sp3)-C(sp3) Coupling",

abstract = "The construction of alkyl-alkyl bonds is a powerful tool in organic synthesis. Redox inversion, defined as switching the donor/acceptor profile of a functional group to its acceptor/donor profile, is used for C(sp3)-C(sp3) coupling. We report a photocatalytic coupling of carboxylic acids to form bibenzyls through a radical-radical coupling. Mechanistic insight is gained through control reactions. This unexplored redox-opposite relationship between a carboxylic acid and its redox-active ester is implemented in catalysis.",

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AU - Roberts, Courtney C.

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AB - The construction of alkyl-alkyl bonds is a powerful tool in organic synthesis. Redox inversion, defined as switching the donor/acceptor profile of a functional group to its acceptor/donor profile, is used for C(sp3)-C(sp3) coupling. We report a photocatalytic coupling of carboxylic acids to form bibenzyls through a radical-radical coupling. Mechanistic insight is gained through control reactions. This unexplored redox-opposite relationship between a carboxylic acid and its redox-active ester is implemented in catalysis.

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