This review highlights the versatility and significance of transition metal-catalyzed cross-coupling reactions employing mild and unique organoindium reagents with exceptional functional group compatibility and sometimes remarkable chemo- and stereoselectivities.

Stereoselective β-C(sp ² )–H alkylation of enamides with N -hydroxyphthalimide esters is demonstrated, affording geometrically defined alkylated enamides bearing various functional groups.

A stereoselective Cu(OTf)₂-mediated C(sp²)–H sulfonylation of enamides with arylsulfonyl radicals generated in situ from DABSO and diazonium salts is developed.