Iodoarene Activation: Take a Leap Forward toward Green and Sustainable Transformations.

Constructing chemical bonds under green sustainable conditions has drawn attention from environmental and economic perspectives. The dissociation of (hetero)aryl-halide bonds is a crucial step of most arylations affording (hetero)arene derivatives. Herein, we summarize the (hetero)aryl halides activation enabling the direct (hetero)arylation of trapping reagents and construction of highly functionalized (hetero)arenes under benign conditions. The strategies for the activation of aryl iodides are classified into (a) hypervalent iodoarene activation followed by functionalization under thermal/photochemical conditions, (b) aryl-I bond dissociation in the presence of bases with/without organic catalysts and promoters, (c) photoinduced aryl-I bond dissociation in the presence/absence of organophotocatalysts, (d) electrochemical activation of aryl iodides by direct/indirect electrolysis mediated by organocatalysts and mediators acting as electron shuttles, and (e) electrophotochemical activation of aryl iodides mediated by redox-active organocatalysts. These activation modes result in aryl iodides exhibiting diverse reactivity as formal aryl cations/radicals/anions and aryne precursors. The coupling of these reactive intermediates with trapping reagents leads to the facile and selective formation of C-C and C-heteroatom bonds. These ecofriendly, inexpensive, and functional group-tolerant activation strategies offer green alternatives to transition metal-based catalysis.