The present work reports, the new route for the synthesis of diarylselenides by coupling of aryltriethoxysilanes with diaryldiselenides. Various ligands were screened for the said coupling in presence of a copper salt. Cu(II)/bpy in DMSO showed excellent activity for the coupling of aryltriethoxysilanes with various diaryldiselenides. In the present work, no fluoride source was used for the activation of aryltriethoxysilanes and also a possible mechanism was proposed for the said reaction. Moreover, diaryldisuphides and diarylditellurides were also effectively coupled with aryltriethoxysilanes using proposed catalytic system. Importantly, use of non‐precious metal based catalytic system, makes the protocol interesting.

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