3 years ago

Rethinking the Dehydrogenative Amide Synthesis

Rethinking the Dehydrogenative Amide Synthesis
Dmitry G. Gusev
This paper is concerned with the mechanism of the catalytic dehydrogenative coupling of primary alcohols with amines; it addresses the question on what happens to the aldehyde produced in the catalytic solution upon dehydrogenation of an alcohol substrate. Here we demonstrate a rapid catalytic reaction of acetaldehyde with primary amines, leading to acetamides. The facile amide bond formation is a low-energy, outer-sphere catalytic process elucidated with the help of DFT calculations. Overall, the dehydrogenative amide synthesis comprises two metal-catalyzed cycles: the first producing the aldehyde and H2, and the second where the hemiaminal is formed and is dehydrogenated. The results call into question the existing mechanistic ideas (reviewed by Li and Hall) that invoke the uncatalyzed formation of a free hemiaminal intermediate and assume that the hemiaminal dehydrogenation requires a 16-electron catalyst.

Publisher URL: http://dx.doi.org/10.1021/acscatal.7b02415

DOI: 10.1021/acscatal.7b02415

You might also like
Discover & Discuss Important Research

Keeping up-to-date with research can feel impossible, with papers being published faster than you'll ever be able to read them. That's where Researcher comes in: we're simplifying discovery and making important discussions happen. With over 19,000 sources, including peer-reviewed journals, preprints, blogs, universities, podcasts and Live events across 10 research areas, you'll never miss what's important to you. It's like social media, but better. Oh, and we should mention - it's free.

  • Download from Google Play
  • Download from App Store
  • Download from AppInChina

Researcher displays publicly available abstracts and doesn’t host any full article content. If the content is open access, we will direct clicks from the abstracts to the publisher website and display the PDF copy on our platform. Clicks to view the full text will be directed to the publisher website, where only users with subscriptions or access through their institution are able to view the full article.