Photoinduced Cu (II)‐Mediated Decarboxylative Thianthrenation of Aryl and Heteroaryl Carboxylic Acids
Abstract: Given that (hetero) aryl carboxylic acids are inexpensive materials available in a great variety from commercial and natural resources or synthesis, the strategies enabling their use as starting materials for preparing fine chemicals are highly sought after. Here we report a photoinduced Cu (II)‐mediated protocol converting (hetero) aryl carboxylic acids into (hetero) aryl thianthrenium salts, high value‐added building blocks that can undergo various subsequent transformations, creating an attractive two‐step pathway for the divergent functionalization of these ubiquitous starting materials. The excellent compatibility of the method is shown by preparing a broad range of sterically and electronically varied (hetero) aryl thianthrenium salts, including derivatives of pharmaceuticals, such as ataluren, celecoxib, flavoxate, probenecid, repaglinide, and tamibarotene. The syntheses of 13 C‐labeled probenecid and bioisosteres of ataluren as well as the unconventional modifications of celecoxib and flavoxate, illustrate the synthetic potential of the strategy. Mechanistic studies are in line with a reaction occurring through a photoinduced ligand‐to‐metal charge transfer (LMCT) of Cu (II)‐arylcarboxylates, enabling radical decarboxylative carbometallation to form arylcopper (II) intermediates that in turn react with thianthrene to form the product. Noteworthy, the susceptibility of aryl thianthrenium salts to photodegradation is overcome by a Cu (I)‐driven salvage loop, which continuously intercepts the transiently formed radicals and regenerates the products.
- Standort
-
Deutsche Nationalbibliothek Frankfurt am Main
- Umfang
-
Online-Ressource
- Sprache
-
Englisch
- Erschienen in
-
Photoinduced Cu (II)‐Mediated Decarboxylative Thianthrenation of Aryl and Heteroaryl Carboxylic Acids ; volume:63 ; number:42 ; year:2024 ; extent:8
Angewandte Chemie / International edition. International edition ; 63, Heft 42 (2024) (gesamt 8)
- Urheber
-
He, Zhen
Dydio, Paweł
- DOI
-
10.1002/anie.202410616
- URN
-
urn:nbn:de:101:1-2410071416167.172889694401
- Rechteinformation
-
Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
- Letzte Aktualisierung
-
15.08.2025, 07:33 MESZ
Datenpartner
Deutsche Nationalbibliothek. Bei Fragen zum Objekt wenden Sie sich bitte an den Datenpartner.
Beteiligte
- He, Zhen
- Dydio, Paweł
Ähnliche Objekte (12)
Photoinduced Cu (II)‐Mediated Decarboxylative Thianthrenation of Aryl and Heteroaryl Carboxylic Acids
Decarboxylative, Radical C–C Bond Formation with Alkyl or Aryl Carboxylic Acids: Recent Advances
Palladium-Catalyzed Cross-Coupling of Aryl Halides with Carboxylic Acids by Photoinduced Reductive Elimination
Photoinduced Triphenylphosphine and Iodide Salt Promoted Reductive Decarboxylative Coupling
Photocatalysis with Cu(II)- and Cu(I)-complexes: Cu(II)-photocatalyzed Decarboxylative Oxygenation of Carboxylic Acids and Cu(I)-photocatalyzed Bromonitroalkylation of Olefins
A General Iron‐Catalyzed Decarboxylative Oxygenation of Aliphatic Carboxylic Acids
A General Iron‐Catalyzed Decarboxylative Oxygenation of Aliphatic Carboxylic Acids
Palladium-Catalyzed Decarboxylative 1,2-Addition of Carboxylic Acids to Glyoxylic Acid Esters
Decarboxylative Iodination of Coumarin‐3‐carboxylic Acids: A Facile Access to 3‐Iodocoumarins
Palladium‐Catalyzed Decarboxylative 1,2‐Addition of Carboxylic Acids to Glyoxylic Acid Esters
Copper-Mediated Synthesis of Monofluoro Aryl Acetates via Decarboxylative Cross-Coupling
Catalytic Photoinduced Intramolecular Decarboxylative and Desulfonylative sp 3 Allylation Enabled by Sulfinate Salts
Photoinduced Cu (II)‐Mediated Decarboxylative Thianthrenation of Aryl and Heteroaryl Carboxylic Acids
Decarboxylative, Radical C–C Bond Formation with Alkyl or Aryl Carboxylic Acids: Recent Advances
Palladium-Catalyzed Cross-Coupling of Aryl Halides with Carboxylic Acids by Photoinduced Reductive Elimination
Photoinduced Triphenylphosphine and Iodide Salt Promoted Reductive Decarboxylative Coupling
Photocatalysis with Cu(II)- and Cu(I)-complexes: Cu(II)-photocatalyzed Decarboxylative Oxygenation of Carboxylic Acids and Cu(I)-photocatalyzed Bromonitroalkylation of Olefins
A General Iron‐Catalyzed Decarboxylative Oxygenation of Aliphatic Carboxylic Acids
A General Iron‐Catalyzed Decarboxylative Oxygenation of Aliphatic Carboxylic Acids
Palladium-Catalyzed Decarboxylative 1,2-Addition of Carboxylic Acids to Glyoxylic Acid Esters
Decarboxylative Iodination of Coumarin‐3‐carboxylic Acids: A Facile Access to 3‐Iodocoumarins
Palladium‐Catalyzed Decarboxylative 1,2‐Addition of Carboxylic Acids to Glyoxylic Acid Esters
Copper-Mediated Synthesis of Monofluoro Aryl Acetates via Decarboxylative Cross-Coupling
Catalytic Photoinduced Intramolecular Decarboxylative and Desulfonylative sp 3 Allylation Enabled by Sulfinate Salts
Photoinduced Cu (II)‐Mediated Decarboxylative Thianthrenation of Aryl and Heteroaryl Carboxylic Acids
Decarboxylative, Radical C–C Bond Formation with Alkyl or Aryl Carboxylic Acids: Recent Advances
Palladium-Catalyzed Cross-Coupling of Aryl Halides with Carboxylic Acids by Photoinduced Reductive Elimination
Photoinduced Triphenylphosphine and Iodide Salt Promoted Reductive Decarboxylative Coupling
Photocatalysis with Cu(II)- and Cu(I)-complexes: Cu(II)-photocatalyzed Decarboxylative Oxygenation of Carboxylic Acids and Cu(I)-photocatalyzed Bromonitroalkylation of Olefins
A General Iron‐Catalyzed Decarboxylative Oxygenation of Aliphatic Carboxylic Acids
A General Iron‐Catalyzed Decarboxylative Oxygenation of Aliphatic Carboxylic Acids
Palladium-Catalyzed Decarboxylative 1,2-Addition of Carboxylic Acids to Glyoxylic Acid Esters
Decarboxylative Iodination of Coumarin‐3‐carboxylic Acids: A Facile Access to 3‐Iodocoumarins
Palladium‐Catalyzed Decarboxylative 1,2‐Addition of Carboxylic Acids to Glyoxylic Acid Esters
Copper-Mediated Synthesis of Monofluoro Aryl Acetates via Decarboxylative Cross-Coupling