An efficient oxidative cycloaddition of enaminones with nitrile oxides generated in situ from respective aldoximes using hypervalent iodine reagents has been developed. Reactions of various aldoximes with enaminones in the presence of [hydroxy(tosyloxy)iodo]benzene involved the regioselective cycloaddition reaction resulting in the formation of the 3,4‐disubstituted isoxazoles in moderate to good yields. Structures of several isoxazole products were confirmed by a single X‐ray crystallography.

A new bicyclic organohypervalent iodine heterocycle derivative of benziodazole was prepared by oxidation of 2-iodo-N,N’-diisopropylisophthalamide with m-chloroperoxybenzoic acid under mild conditions. Single crystal X-ray crystallography of this compound revealed a five-membered bis-heterocyclic structure with two covalent bonds between the iodine atom and the nitrogen atoms. This novel benziodazole is a very stable compound with good solubility in common organic solvents. This compound can be used as an efficient reagent for oxidatively assisted coupling of carboxylic acids with alcohols or amines to afford the corresponding esters or amides in moderate yields.

A new practical procedure of imination for sulfide has been developed. The treatment of (N-tosylimino)-phenyl-λ3-iodane, PhINTs, with various sulfides in the presence of a catalytic amount of I2 under metal-free conditions affords the corresponding N-tosylsulfilimine compounds with moderate to good yields. This facile transfer procedure of the sulfonylimino group can also be applied to triphenylphosphine to produce the respective iminotriphenylphosphoranes in high yields. According to the reaction mechanism studies, the process of imination from (N-tosylimino)-phenyl-λ3-iodane to sulfide under the conditions may involve radical steps within the reaction mechanism.