: In the past several decades, hypervalent iodine chemistry has witnessed prosperous development as hypervalent iodine reagents have been widely used in various organic transformations. Specifically, hypervalent iodine reagents have been vastly used in various bond-forming reactions. Among these oxidative coupling reactions, the reactions involving the formation of C-N bond have been extensively explored to construct various heterocyclic skeletons and synthesize various useful building blocks. This review article is to summarize all the transformations in which carbon-nitrogen bond formation occurred by using hypervalent iodine reagents under metal-free conditions.

A phenyliodine(III) diacetate (PIDA)/CuBr‐mediated construction of the novel 3H,3'H‐spiro[benzofuran‐2,2'‐benzo[b]thiophene]‐3,3'‐dione skeleton was realized from the reaction of (Z)‐3‐hydroxy‐1‐(2‐hydroxyphenyl)‐3‐(2‐halogenphenyl)prop‐2‐en‐1‐ones with potassium ethylxanthate in the presence of 1,10‐phen. The reaction sequence was postulated to encompass a PIDA‐mediated oxidative C–O bond formation followed by a CuBr‐mediated spirocyclization step.