An environmentally friendly strategy for the photocatalyzed three-component reaction between quinoxalinones, alkenes, and hypervalent iodine­(III) reagents is disclosed. The new designed difluoroiodane­(III) reagent shows excellent reactivity, providing a wide range of difluoroalkyl-substituted quinoxaline-2­(1H)-ones in moderate to excellent yields under mild conditions. Experimental studies demonstrated that a difluoroalkyl radical intermediate was involved in this reaction.

A series of novel fluoro‐containing hypervalent iodane (III) reagents was designed and synthesized. By employing these novel hypervalent iodane (III) reagents, an efficient visible‐light‐triggered radical cyclization of alkynoates to diversely 3‐fluoroalkylated coumarins was developed under metal free condition. It provided an alternative and environmental friendly approach for the installation of 3‐fluoroalkyl motif into synthetically valuable building block coumarins.

A visible-light-induced difluoroalkylation of unactivated alkenes by fluoro-containing hypervalent iodine-based difluoroalkylation reagent was achieved for the first time under photo-catalyst-free conditions. Moreover, the same reaction conditions were applicable to the difluoroalkylation of alkynes to give the hydrodifluoroalkylation products in moderate to excellent yields. The readily available reagent, broad substrate scope, and photo-catalyst-free conditions make this protocol an efficient and environmental friendly method for the hydrodifluoroalkylation of alkenes and alkynes.