“Nitrogen-Centered Radical-Directed C(sp³)−H Amination and Aminoalkylation Using (Diarylmethylene)amino Benziodoxolones"
Kensuke Kiyokawa*, Mari Sugimura, Megumi Abe, Daiki Wada, Hikaru Kaneba, and Satoshi Minakata*
ChemistryEurope 2025, , e202500188. DOI:10.1002/ceur.202500188

Abstract: Intermolecular C(sp³)−H functionalization via nitrogen-centered radical-directed 1,5-hydrogen atom transfer (HAT) is a powerful strategy for rapidly constructing functionalized molecules. Despite the obvious potential, applying this approach to aminofunctionalization remains challenging. Herein, a photochemical method is reported for C(sp³)−H aminofunctionalization that is achieved using hypervalent iodine-based aminating reagents—(diarylmethylene)amino benziodoxolones (DABXs). These reagents act as both single-electron oxidants and sources of nitrogen-based SOMOphiles (iminyl radicals), which enables the site-selective amination and aminoalkylation of α-aminoxy acid derivatives via 1,5-HAT. Notably, this reaction proceeds efficiently under mild reaction conditions without external photosensitizers to offer a practical and versatile method for the syntheses of readily modifiable diamines and aminoamides.

“Iodine-Catalyzed Stereospecific anti-Diamination of trans-β-Methylstyrene"
Takeshi Sugiyama, Chiyuki Naito, and Satoshi Minakata*
Org. Synth. 2025, 102, 203–216. DOI:10.15227/orgsyn.102.0203

Abstract: In this study, we developed an environmentally friendly synthetic method that achieves the stereospecific anti-diamination of trans-β-methylstyrene with high selectivity and yield, utilizing an iodine catalyst and sodium hypochlorite pentahydrate.

“Photoinduced Azidoamination of Styrenes Using Sodium Azide and (Diphenylmethylene)amino Benziodoxolone"
Kensuke Kiyokawa*, Koki Nakano, Daichi Okumura, and Satoshi Minakata*
Chem. Asian J. 2025, 20, e202401493/1–4. DOI:10.1002/asia.202401493

Abstract: Herein, we report the radical azidoamination of styrenes via the use of a combination of sodium azide and (diphenylmethylene)amino benziodoxolone under visible-light irradiation. This approach to unsymmetrical diamination provides a simple and practical method for constructing vicinal diamine scaffolds with two distinct and easily modifiable amino functionalities.