Photoinduced Cu (II)‐Mediated Decarboxylative Thianthrenation of Aryl and Heteroaryl Carboxylic Acids

to related objects

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.

Location: Deutsche Nationalbibliothek Frankfurt am Main

Extent: Online-Ressource

Language: Englisch

Bibliographic citation: Photoinduced Cu (II)‐Mediated Decarboxylative Thianthrenation of Aryl and Heteroaryl Carboxylic Acids ; volume:136 ; number:42 ; year:2024 ; extent:8
Angewandte Chemie ; 136, Heft 42 (2024) (gesamt 8)

Creator: He, Zhen
Dydio, Paweł

DOI: 10.1002/ange.202410616

URN: urn:nbn:de:101:1-2410071428206.896152410952

Rights: Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.

Last update: 15.08.2025, 7:39 AM CEST

Data provider

This object is provided by:
Deutsche Nationalbibliothek. If you have any questions about the object, please contact the data provider.

Show original at data provider

Associated

He, Zhen
Dydio, Paweł

Other Objects (12)

Photoinduced Cu (II)‐Mediated Decarboxylative Thianthrenation of Aryl and Heteroaryl Carboxylic Acids

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

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

Palladium-Catalyzed Cross-Coupling of Aryl Halides with Carboxylic Acids by Photoinduced Reductive Elimination

Photoinduced Triphenylphosphine and Iodide Salt Promoted Reductive Decarboxylative Coupling

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

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

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

Palladium-Catalyzed Decarboxylative 1,2-Addition of Carboxylic Acids to Glyoxylic Acid Esters

Palladium‐Catalyzed Decarboxylative 1,2‐Addition of Carboxylic Acids to Glyoxylic Acid Esters

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

Decarboxylative Iodination of Coumarin‐3‐carboxylic Acids: A Facile Access to 3‐Iodocoumarins

Copper-Mediated Synthesis of Monofluoro Aryl Acetates via Decarboxylative Cross-Coupling

Copper-Mediated Synthesis of Monofluoro Aryl Acetates via Decarboxylative Cross-Coupling

Catalytic Photoinduced Intramolecular Decarboxylative and Desulfonylative sp 3 Allylation Enabled by Sulfinate Salts

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

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

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

Palladium-Catalyzed Cross-Coupling of Aryl Halides with Carboxylic Acids by Photoinduced Reductive Elimination

Photoinduced Triphenylphosphine and Iodide Salt Promoted Reductive Decarboxylative Coupling

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

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

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

Palladium-Catalyzed Decarboxylative 1,2-Addition of Carboxylic Acids to Glyoxylic Acid Esters

Palladium‐Catalyzed Decarboxylative 1,2‐Addition of Carboxylic Acids to Glyoxylic Acid Esters

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

Decarboxylative Iodination of Coumarin‐3‐carboxylic Acids: A Facile Access to 3‐Iodocoumarins

Copper-Mediated Synthesis of Monofluoro Aryl Acetates via Decarboxylative Cross-Coupling

Copper-Mediated Synthesis of Monofluoro Aryl Acetates via Decarboxylative Cross-Coupling

Catalytic Photoinduced Intramolecular Decarboxylative and Desulfonylative sp 3 Allylation Enabled by Sulfinate Salts

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

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

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

Palladium-Catalyzed Cross-Coupling of Aryl Halides with Carboxylic Acids by Photoinduced Reductive Elimination

Photoinduced Triphenylphosphine and Iodide Salt Promoted Reductive Decarboxylative Coupling

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

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

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

Palladium-Catalyzed Decarboxylative 1,2-Addition of Carboxylic Acids to Glyoxylic Acid Esters

Palladium‐Catalyzed Decarboxylative 1,2‐Addition of Carboxylic Acids to Glyoxylic Acid Esters

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

Decarboxylative Iodination of Coumarin‐3‐carboxylic Acids: A Facile Access to 3‐Iodocoumarins

Copper-Mediated Synthesis of Monofluoro Aryl Acetates via Decarboxylative Cross-Coupling

Copper-Mediated Synthesis of Monofluoro Aryl Acetates via Decarboxylative Cross-Coupling

Catalytic Photoinduced Intramolecular Decarboxylative and Desulfonylative sp 3 Allylation Enabled by Sulfinate Salts

Catalytic Photoinduced Intramolecular Decarboxylative and Desulfonylative sp 3 Allylation Enabled by Sulfinate Salts

Cultural heritage institutions wishing to register will find more information here.

Fields marked * need to be filled in.

Username*

Please enter your username

Email*

Please enter your email address

Please do not fill this field

First name

Last name

Password*

Please enter your password

Confirm password*

Please enter the same password

I have read the terms of use and the privacy policy for the collection of personal data and accept them. *

This field is required.

I would like to subscribe to the newsletter of the Deutsche Digitale Bibliothek. See newsletter subscription info.

Account created

Your "My DDB" account has been successfully created. Before you can log in to your account, you must click the confirmation link in the message we just sent to the email address you provided.