3 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

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