2020 journal article

Identification of key functionalization species in the Cp*Ir(iii)-catalyzed-ortho halogenation of benzamides

Dalton Transactions, 49(45), 16166–16174.

By: A. Guzmán Santiago n, C. Brown n, R. Sommer n & E. Ison n

co-author countries: United States of America 🇺🇸
Source: Crossref
Added: December 21, 2020

Cp*Ir(iii) complexes have been shown to be effective for the halogenation of N,N-diisopropylbenzamides with N-halosuccinimide as a suitable halogen source. The optimized conditions for the iodination reaction consist of 0.5 mol% [Cp*IrCl2]2 in 1,2-dichloroethane at 60 °C for 1 h to form a variety of iodinated benzamides in high yields. Increasing the catalyst loading to 6 mol% and the time to 4 h enabled the bromination reaction of the same substrates. 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 studies showed the reaction dependence is first order in iridium, positive order in benzamide, and zero order in N-iodosuccinimide. A KIE of 2.5 was obtained from an independent H/D kinetic isotope effect study. Computational studies (DFT-BP3PW91) indicate that a CMD mechanism is more likely than an oxidative addition pathway for the C-H bond activation step. The calculated functionalization step involves an Ir(v) species that is the result of oxidative addition of acetate hypoiodite that is generated in situ from N-iodosuccinimide and acetic acid.