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

12 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

Publisher link

10.1021/acs.joc.2c02877

Find It

Find It at U of M Libraries

Cite this

@article{e67e8028574a403abddd1ebed9b8f1c1,

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.",

author = "Seong, \{Chris M.\} and Ansel, \{Annabel Q.\} and Roberts, \{Courtney C.\}",

note = "Publisher Copyright: {\textcopyright} 2023 American Chemical Society",

year = "2023",

month = mar,

day = "17",

doi = "10.1021/acs.joc.2c02877",

language = "English (US)",

volume = "88",

pages = "3935--3940",

journal = "Journal of Organic Chemistry",

issn = "0022-3263",

publisher = "American Chemical Society",

number = "6",

}

TY - JOUR

T1 - Redox Inversion

T2 - A Radical Analogue of Umpolung Reactivity for Base- and Metal-Free Catalytic C(sp3)-C(sp3) Coupling

AU - Seong, Chris M.

AU - Ansel, Annabel Q.

AU - Roberts, Courtney C.

PY - 2023/3/17

Y1 - 2023/3/17

N2 - 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.

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.

UR - https://www.scopus.com/pages/publications/85149724533

UR - https://www.scopus.com/pages/publications/85149724533#tab=citedBy

U2 - 10.1021/acs.joc.2c02877

DO - 10.1021/acs.joc.2c02877

M3 - Article

C2 - 36877204

AN - SCOPUS:85149724533

SN - 0022-3263

VL - 88

SP - 3935

EP - 3940

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

IS - 6

ER -