Charge-Transfer Complex Promoted C-N Bond Activation for Ni-Catalyzed Carbonylation

A new strategy was developed for activation of C-N bond via formation of an amineI(2) charge-transfer complex, which facilitates the inert C-N bond activation via oxidative addition with Ni(0). This strategy has been successfully applied in the Ni-catalyzed carbonylation of benzylamines via direct insertion of CO into the C-N bond, which provided a straightforward and rapid approach to arylacetamides in the presence of catalytic amounts of I-2 and Ni-catalyst. Mechanistic studies suggested that a benzyl radical generated via the oxidative addition was involved in the present reaction.