Exploring nickel-catalyzed organochalcogen synthesis cross-coupling of benzonitrile and alkyl chalcogenols with computational tools.

The preparation of organochalcogens has increased in recent times due to their promising biological activity properties. This work studies the reaction mechanism of a nickel(0)-catalyzed cross-coupling between benzonitrile and propanethiol to produce new C-S bonds by computational means. The proposed mechanism follows the classical oxidative addition/transmetalation/reductive elimination cross-coupling sequence, involving an unusual oxidative addition of a Ph-CN bond onto the active species. The computed catalytic cycle for thioether synthesis has been examined to determine whether the same protocol could be employed to build the analogous C-Se and C-Te bonds. The proposed mechanism for C-S coupling is validated by microkinetic modeling and shows a very good agreement with available experimental data. The extension of the proposed mechanism to C-Se and C-Te couplings indicates that these new reactions should be operative, although their reaction rates appear to be significantly slower.