Ruthenium‐Catalyzed Reductive Arylation of N‐(2‐Pyridinyl)amides with Isopropanol and Arylboronate Esters

• Published in: Angewandte Chemie Vol. 131; no. 2; pp. 492 - 497
• Main Authors: Ronson, Thomas O., Renders, Evelien, Van Steijvoort, Ben F., Wang, Xubin, Wybon, Clarence C. D., Prokopcová, Hana, Meerpoel, Lieven, Maes, Bert U. W.
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 08.01.2019
• Subjects: Amide; Amides; Amine; Aromatic compounds; Arylierung; Carboxylic acids; Chemical reactions; Chemistry; Esters; Mehrkomponenten-Reaktionen; Organochlorine compounds; Reaction products; Ruthenium; Substitution reactions; Substrates
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.201810947

A new three‐component reductive arylation of amides with stable reactants (iPrOH and arylboronate esters), making use of a 2‐pyridinyl (Py) directing group, is described. The N‐Py‐amide substrates are readily prepared from carboxylic acids and PyNH2, and the resulting N‐Py‐1‐arylalkanamine reaction products are easily transformed into the corresponding chlorides by substitution of the HN‐Py group with HCl. The 1‐aryl‐1‐chloroalkane products allow substitution and cross‐coupling reactions. Therefore, a general protocol for the transformation of carboxylic acids into a variety of functionalities is obtained. The Py‐NH2 by‐product can be recycled. Eine reduktive Dreikomponenten‐Arylierung von Amiden mit stabilen Reaktanten (iPrOH und Arylboratester) in Gegenwart einer dirigierenden 2‐Pyridinyl(py)‐Gruppe (DG) wird beschrieben. Die N‐Py‐Amide lassen sich leicht aus Carbonsäuren herstellen, und die resultierenden N‐Py‐1‐Arylalkanamine können durch Substitution der HN‐Py‐Gruppe durch HCl leicht in die entsprechenden Chloride überführt werden.