An efficient PIDA (phenyliodine(III) diacetate)-promoted positional selective CÀ H selenylations of indolines with diaryl diselenides has been developed. This transformation conducted under mild reaction conditions with a broad functional group tolerance, thus providing an efficient protocol to selenylated indolines. Preliminary mechanistic studies indicated a SET pathway was likely involved in this selenylation reaction.

This review summarizes recent advances in C–S and C–Se formations via transition metal-catalyzed C–H functionalization utilizing directing groups to control the site-selectivity.

Ruthenium-catalyzed CÀH chalcogenations of anilides with readily available diselenides and disulfides have been achieved. Our strategy features ample substrate scope, affording the mono-ortho selenylated and thiolated anilides with complete site selectivity control and high catalytic efficacy. Detailed mechanistic studies provide strong support for a facile base-assisted internal electrophilic substitution (BIES) metalation event.

A convenient and effective protocol for the ruthenium‐catalyzed C–H selenylations of benzamide was achieved under mild reaction conditions. The robust ruthenium catalyst tolerated a wide range of functional groups and set the stage for the preparation for diversely decorated benzamides. The amide directing group could be transferred to carboxylic acid, aldehyde and tetrazoles. Preliminary mechanistic study indicated a base‐assisted electrophilic‐type substitution C–H activation event.