Halogenated arenes are a key feature in many agrochemicals, pharmaceuticals and natural products. Despite their relevance, and the variety of catalytic methodologies to access these compounds, there is a lack of mechanistic understanding. Cp*Ir(III) complexes have been shown to be effective for the catalytic halogenation of N,N-diisopropylbenzamides with N-halosuccinimide as a suitable halogen source in high yields. Reactivity was not observed for the chlorination of these substrates. A variety of functional groups on the para-position of the benzamide were well tolerated. Kinetic and computational studies (DFT-BP3PW91) indicate that a CMD mechanism is more likely than an oxidative addition pathway for the C–H bond activation step. Moreover, the calculated functionalization step involves an Ir(V) species resulting from oxidative addition of a haloacetate species, that is generated in situ from N-halosuccinimide and acetic acid, and is the active species in the catalytic reaction.

Identification of key functionalization species in the Cp*Ir(III)-catalyzed-<i>ortho </i>halogenation of benzamides

Macromolecular Chemistry: The Second Century

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Identification of key functionalization species in the Cp*Ir(III)-catalyzed-ortho halogenation of benzamides

Identification of key functionalization species in the CpIr(III)-catalyzed-ortho* halogenation of benzamides