Azidoiodinanes 2 and 4a,b can be prepared from the appropriate benziodoxoles 1 and 3a,b and trimethylsilyl azide in the form of stable, crystalline compounds. A single-crystal X-ray analysis for azide 4b revealed the expected hypervalent iodine distorted T-shaped geometry with the N1−I−O bond angle of 169.5 (2) degrees. The lengths of the bonds to the iodine atom, I−N (2.18 Å), I−O (2.13 Å), and I−C (2.11 Å), are within the range of typical single covalent bonds in organic derivatives of polyvalent iodine, while the previously reported benziodoxoles generally have an elongated I−O bond. The geometry of the I(III)NNN fragment in 4b is similar to the literature electron diffraction data on monomeric iodine azide, IN3, in gas phase. Azidobenziodoxoles 2,4 are potentially useful reagents for direct azidation of organic substrates, such as dimethylanilines, alkanes, and alkenes. Reaction of 2 with dimethylanilines proceeds under mild conditions to afford the respective N-azidomethyl-N-methylanilines in excellent yield. Alkanes, cycloalkanes, and adamantanes react with azidobenziodoxoles 2 or 4b in the presence of radical initiators at 80−132 °C with the formation of tertiary alkylazides, while reaction of norbornane leads to exo-2-azidonorbornane. Under similar conditions cyclohexene is selectively azidated at the allylic position.

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The five-membered iodine-oxygen heterocycles, benziodoxoles (1), have recently attracted significant interest due to their excellent catalytic activity in the cleavage of toxic phosphates and several useful applications as reagents for organic synthesis. 1 The analogous iodine-nitrogen heterocycles, benziodazoles (2), have received much less attention. 2-6 The most important and readily available is the acetate derivative of benziodazole. In particular, Moss and co-workers have found that acetoxybenziodazole has a minimal catalytic activity in the cleavage of a model phosphotriester under basic conditions. 3 Acetoxybenziodazole was first prepared in 1965 by peracetic oxidation of 2-iodobenzamide. 2 Based on the IR spectroscopy, the authors 2 assigned the structure of N-acetyl-1-hydroxy-3-(1H)-1,2-benziodazole-3-one (3) for this compound. Structure 3 was also adopted in the more recent studies. [3][4][5]

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