Diversification of Aryl Sulfonyl Compounds through Ligand‐Controlledmeta‐ andpara‐C−H Borylation

Abstract

Aryl sulfones and aryl sulfonamides are of great importance in organic synthesis and medicinal chemistry. Although ortho‐C−H functionalization of aryl sulfonyl compounds has been extensively explored, the functionalization of remote meta‐ and para‐C−H bonds is very rare. Herein, we report a tunable meta‐ and para‐selective C−H borylation of aryl sulfonyl compounds enabled by computationally designed ligands and iridium catalyst. This method is capable of accommodating a broad range of substrates under mild reaction conditions. Gram‐scale preparation can be achieved with iridium catalyst loading as low as 0.1 mol%. As the introduced boronate group can be easily converted into many other groups, our method provides a general solution to installing functional groups at either meta‐ or para‐position of aryl sulfones and aryl sulfonamides with good to excellent selectivity.

Adamantane-1-Carbonyl-Directed C–H Borylation and Hydroxylation of Benzenethiols

“…With the development of boron chemistry, C–H borylation provides a practical strategy to achieve this goal, since the C–B bond is easily converted into a great variety of useful functional groups. However, the borylation of sulfur-containing compounds is concentrated in the aryl sulfides and sulfones . The direct C–H borylation of benzenethiols is far less developed mainly due to the highly toxic and low reactivity .…”