5 years ago

Mechanism-Driven Approach To Develop a Mild and Versatile C−H Amidation through IrIII Catalysis

Mechanism-Driven Approach To Develop a Mild and Versatile C−H Amidation through IrIII Catalysis
Yeongyu Hwang, Sukbok Chang, Yoonsu Park
Described herein is a mechanism-based approach to develop a versatile C−H amidation protocol under IrIII catalysis. Reaction kinetics of a key C−N coupling step with acyl azide and 1,4,2-dioxazol-5-one led us to conclude that dioxazolones are much more efficient in mediating the formation of a carbon−nitrogen bond from an iridacyclic intermediate. Computational analysis revealed that the origin of higher reactivity is asynchronous decarboxylation motion, which may facilitate the formation of Ir-imido species. Importantly, stoichiometric reactivity was successfully translated into catalytic activity with a broad range of substrates (18 different types), many of which are regarded as challenging to functionalize. Application of the new method enables late-stage functionalization of drug molecules. All in the timing: The presence of an asynchronous transition state was identified as being crucial for an efficient amidating agent in catalytic C−H amidation. Combined reaction kinetics and theoretical studies guided the development of versatile IrIII catalysis with various challenging substrates, including late-stage functionalization of drug molecules (see scheme).

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201702397

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.