2023
DOI: 10.1039/d3gc01299a
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Photocatalytic defluorocarboxylation using formate salts as both a reductant and a carbon dioxide source

Abstract: Herein, we report a photocatalytic defluorocarboxylation of benzylic C(sp3)−F bonds using formate salts as both reductant and carbon dioxide source. A variety of benzyl fluorides, bearing primary or secondary C(sp3)−F...

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Cited by 5 publications
(3 citation statements)
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References 76 publications
(26 reference statements)
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“…The carbon dioxide radical anion (CO 2 •− ) intermediate, [ 23‐32 ] which can be generated in situ by hydrogen atom transfer (HAT) with formic acid salts and a thiol radical, [ 33‐36 ] is an attractive reactive radical species and has shown wide utility in organic synthesis. Due to its negative reduction potential, CO 2 •− ( E 1/2 ° = −2.2 V vs SCE) has been used to activate a wide range of challenging chemical bonds ( e.g ., aryl chlorides, aryl bromides, benzyl C‐F, etc .)…”
Section: Background and Originality Contentmentioning
confidence: 99%
“…The carbon dioxide radical anion (CO 2 •− ) intermediate, [ 23‐32 ] which can be generated in situ by hydrogen atom transfer (HAT) with formic acid salts and a thiol radical, [ 33‐36 ] is an attractive reactive radical species and has shown wide utility in organic synthesis. Due to its negative reduction potential, CO 2 •− ( E 1/2 ° = −2.2 V vs SCE) has been used to activate a wide range of challenging chemical bonds ( e.g ., aryl chlorides, aryl bromides, benzyl C‐F, etc .)…”
Section: Background and Originality Contentmentioning
confidence: 99%
“…The traditional synthetic protocol of ibuprofen involves the Boots-Hoechst-Celanese process from the corresponding benzyl alcohol in the presence of a palladium catalyst and high-pressure CO as the carbonyl (C1) source . More mild, efficient, and sustainable protocols to access such molecules in metal-free conditions are highly desired and attractive for the past decades . Development of different activation groups and C–O bond cleavage processes to install the carboxyl group are key challenges.…”
Section: Introductionmentioning
confidence: 99%
“…1 Among these benefits, the attractiveness lies in its ability to serve as a green one-carbon (C1) structural unit, which is more practical compared to its gaseous alternatives. 2 Until now, alkene hydrocarboxylation with formate has particularly benefited from extensive innovation. In this process, the in situ generation of carbon dioxide radical anions (CO 2 ˙ − ) ( E 1/2 = −2.2 V vs. SCE) 3 serves as a nucleophilic carbon-partner under mild conditions, allowing for transformations involving polarity matched hydrogen atom transfer (HAT), which has been widely explored.…”
mentioning
confidence: 99%