The mechanism of directed Ni(ii)-catalyzed C-H iodination with molecular iodine.

ABSTRACT: The density functional theory method is used to elucidate the elementary steps of Ni(ii)-catalyzed C(sp²)-H iodination with I₂ and substrates bearing N,N'-bidentate directing centers, amide-oxazoline (AO) and 8-aminoquinoline (AQ). The relative stability of the lowest energy high- and low-spin electronic states of the catalyst and intermediates is found to be an important factor for all of the steps in the reaction. As a result, two-state reactivity for these systems is reported, where the reaction is initiated on the triplet surface and generates a high energy singlet nickelacycle. It is shown that the addition of Na₂CO₃ base to the reaction mixture facilitates C-H activation. The presence of I₂ in the reaction provides

SUBMITTER: Haines BE 

PROVIDER: S-EPMC5883947 | biostudies-literature | 2018 Feb

REPOSITORIES: biostudies-literature