Metallacycle-Catalyzed SNAr Reaction in Water: Supramolecular Inhibition by Means of Host–Guest Complexation

Eva M. López-Vidal, Antonio Fernández-Mato, Marcos D. García, Moisés Pérez-Lorenzo, Carlos Peinador, and José M. Quintela

J. Org. Chem. 2014, 79, 1265‒1270

The performance of a PtII diazapyrenium-based metallacycle as a reusable substoichiometric catalyst for the SNAr reaction between halodinitrobenzenes and sodium azide at rt in aqueous media is reported. The results suggest that the catalytic effect is promoted by the association of the azide to the diazapyrenium cationic subunits of the catalyst. The findings demonstrate that the formation of an inclusion complex between pyrene and the metallacycle has a regulatory effect over the system, resulting in allosteric-like inhibition of the SNAr reaction.