Elucidating chemical reactivity and transition state of mononuclear rearrangement of heterocycles through the use of compartimentalized micellar media

• Micelles allow to perform mononuclear rearrangement (MRH) of heterocycles in water.
• Micelles allow to clarify the interplay of two opposite factors.
• In charged micelles MRH is driven by the acidity of the nitrogen-bonded proton.
• In aprotic micelles nitrogen nucleophilicity and NN bond formation drive the MRH.

The present comprehensive kinetic investigation in micellar systems deepens and broadens the knowledge of mononuclear rearrangement of heterocycles (MRH) of Z-phenylhydrazone of 3-benzoyl-5-phenyl-1,2,4-oxadiazole, reaction already carried out in different reaction media. As a matter of fact the use of four types of micelles different for charge, shape and polarity has allowed us to evaluate the role of micellar systems, as reaction media, on the rate of MRH and to quantify their catalytic effect. Moreover, the data obtained have enabled us to draw some intriguing conclusions on the localization of the substrate in the micelles, the transition state structure and the driving force of the reaction.

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