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Updated: Jun 3, 2025
Efficient Synthesis of All-Carbon Quaternary Centers via the Conjugate Addition of Functionalized Monoorganozinc Bromides
Published on: May 26, 2019
Exploring nickel-catalyzed organochalcogen synthesis via cross-coupling of benzonitrile and alkyl chalcogenols with
Francisco A Gómez-Mudarra1,2, Gabriel Aullón1,2, Jesús Jover1,2
1Secció de Química Inorgànica, Departament de Química Inorgànica i Orgànica, Universitat de Barcelona, Martí i Franquès 1-11, 08028, Barcelona, Spain. jjovermo@ub.edu.
Abstract:
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.
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