A joint experimental and theoretical study of kinetic and mechanism of rearrangement of allylp-tolyl ether

A typical organic reaction proceeds in a special mechanism. Theremay be many proposed mechanisms for a typical organic reaction.Experimental methods have many instrumental limitations such astrapping the intermediates or transition states (TSs) in confirming themechanism that reactions proceed from it. Computational methodscan make confirming the mechanism easer, cheaper and exacter.We solved such an example in order to confirm and detailed study ofthe rearrangement mechanism of allyl p-tolyl ether (Scheme 1). Therearrangement of allyl p-tolyl ether may proceed in two differentmechanisms: (i) a concerted mechanism in which the transition stateforms in one-step (Claisen rearrangement) and (ii) a stepwisemechanism, involving forming a radical as the intermediate. The firstone is one of the pericyclic mechanisms. Pericyclic reactions haverelatively nonpolar TSs with considerable cyclic delocalizationreferred to as aromatic character.