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 amine–I2 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 I2 and Ni catalyst. Mechanistic studies suggested that
a benzyl radical generated via the oxidative addition was involved
in the present reaction.