A metal- and base-free method is developed for the synthesis of aryl iodides from arylhydrazine hydrochlorides and iodine. A wide variety of aryl iodides can be conveniently synthesized by an equimolar reaction of arylhydrazine hydrochlorides and I 2 in dimethyl sulfoxide at 60 °C for 6 h. In the iodination step, arylhydrazines are oxidized by iodine to form arenediazonium salts, which undergo single-electron transfer from iodide anion to give aryl and iodine radicals; subsequent combination of them affords the corresponding aryl iodides.

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Despite the promising pharmacological activity and material properties of five-membered heterocyclic compounds containing phosphorus and nitrogen, synthetic examples of them have been rather limited due to the instability of phosphorus toward air and water. In this study, 1,3-benzoazaphosphol analogues were selected as target molecules, and various synthetic routes were examined to establish a fundamental technology for the introduction of phosphorus groups into aromatic rings and formation of five-membered rings containing phosphorus and nitrogen by cyclization. As a result, we found that 2-aminophenyl(phenyl)phosphine is an extremely promising synthetic intermediate with high stability and easy handling. Furthermore, 2-methyl-3-phenyl-2,3-dihydro-1H-benzo[d][1,3]azaphosphole and 3-phenyl-2,3-dihydro-1H-benzo[d][1,3]azaphosphole-2-thione as synthetically useful 1,3-benzoazaphosphol analogues were successfully synthesized by using 2-aminophenyl(phenyl)phosphine as a key intermediate.