Kazuo Nagasawa

Iodine and its hypervalent derivatives have emerged as versatile and environmentally friendly oxidative reagents in organic synthesis, offering efficient ways to form new bonds. However, the use of hypervalent iodine reagents is challenging, as they are unstable, potentially explosive, and costly. Therefore, hypoiodite species derived from onium iodites using safe and inexpensive oxidants are considered more promising for facilitating oxidative transformations. Nevertheless, applications of such catalytic systems are still limited in scope, especially for asymmetric reactions. In this concept paper, we described recent progress in chiral hypoiodite‐catalyzed enantioselective oxidative bond‐forming reactions, focusing on carbon–oxygen, carbon–nitrogen, and carbon–carbon bond formation reactions using ammonium and guanidinium salts as onium iodites.