Cyclodextrin induced switch between heterolytic and homolytic dediazoniation mechanisms

► We studied the reaction of 4-nitrobenzenediazonium ions with cyclodextrins at pH < 3. ► In the absence of cyclodextrin, the main reaction pathway is heterolytic DN + AN mechanism. ► Addition of cyclodextrin increases the rate of reaction and promotes homolytic dediazoniation. ► Addition of sodium dodecylsulfate blocks the cyclodextrin cavity inhibiting the reaction.