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.

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.

An efficient ruthenium-catalyzed direct C−H selenylation of aryl acetic amides and esters has been achieved via distal weakly coordination. Notable features of this protocol including broad substrate scope, wide functional group tolerance, and good regioselectivity. In addition, diaryl disulfides were also successfully applied to this reaction under slightly modified conditions.

The first palladium(II)‐catalyzed direct ortho‐C(sp2)–H chalcogenations of N‐arylsulfonamide via weak coordination have been achieved, affording the corresponding mono‐chalocgenated products in good to excellent yields. This strategy features ligand/additive‐free conditions, broad substrate scope with excellent functional group tolerance and a high position selectivity.