Carbon Monoxide Free Aminocarbonylation of Aryl and Alkenyl Iodides Using DMF as an Amide Source

Kazushi Hosoi, Kyoko Nozaki* and Tamejiro Hiyama

*Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan, Email: nozakichembio.t.u-tokyo.ac.jp

K. Hosoi, K. Nozaki, T. Hiyama, Org. Lett., 2002, 4, 2849-2851.

DOI: 10.1021/ol026236k

Abstract

Tertiary amides can be synthesized by a palladium-catalyzed coupling of N,N-dimethylformamide with aryl or alkenyl halides in the presence of phosphoryl chloride.

proposed mechanism

Details

The document discusses a novel method for the carbon monoxide-free aminocarbonylation of aryl and alkenyl iodides using N,N-dimethylformamide (DMF) as an amide source. This reaction, catalyzed by palladium and facilitated by phosphoryl chloride (POCl₃), produces tertiary amides in good yields. Unlike previous methods that required carbon monoxide, this approach eliminates the need for CO, making it safer and more practical. The reaction mechanism likely involves the formation of an imminium species from DMF and POCl₃, followed by a Heck-type addition of aryl halides. The study demonstrates that various aryl iodides, including those with electron-withdrawing or electron-donating groups, can undergo this transformation efficiently. The method is specific to DMF, as other amides and aldehydes did not yield the desired products. This research provides a significant advancement in the field of organic synthesis by offering a more convenient and less hazardous route to arylcarboxamides. The work was supported by the Ministry of Education, Science, Sports, and Culture of Japan, and detailed experimental procedures and product characterizations are available online.

Key Words

Benzamides, Aminocarbonylation

ID: J54-Y2002-360