Palladium-Catalysed Reductive Aminocarbonylation of Aryl Bromides and Iodides with Nitroarenes

Abstract

Amide functional groups are a structural feature in a vast array of beneficial organic molecules. This has resulted in a surge in new methodologies developed to enable access to this functional group using a broad range of coupling partners. Herein, we report a palladium-catalysed reductive aminocarbonylation of aryl bromides and iodides with nitroarenes to afford the respective amide products. The developed protocol employs Mo(CO)6 as a carbonyl source and a combination of Zn and TMSCl as co-reducing agents. For most substrates, the anticipated amide products were obtained in modest to high amide product yields.

Direct formation of amide/peptide bonds from carboxylic acids: no traditional coupling reagents, 1-pot, and green

“…Particularly noteworthy is the well-known early warning on the explosiveness of HOBt, and the more recent report by Nowick and co-workers 4 highlighting the non-trivial safety issues (especially anaphylaxis) that surround use of common uronium couplings agents HATU, HBTU, and HCTU. Thus, while applications of these dehydrating agents continue to appear unabated due to the importance of the amide/peptide unit, there is more than ample justification for devising alternatives that avoid these issues in their entirety; 5 indeed, a truly green chemical solution applicable to highly functionalized molecules and that can be used in a sequential fashion in the same reaction vessel seems long overdue. 6 …”