nN → π*Ar interactions stabilize the E-ac isomers of arylhydrazides and facilitate their SNAr autocyclizations

Abstract

We describe a novel mechanism of stabilization of the E-ac isomer of an arylhydrazide via n_N → π*_Ar interactions. We further show that when a leaving group (F) is present at the ortho-position of the carbonyl group of such an arylhydrazide, the n_N → π*_Ar interaction facilitates an S_NAr autocyclization reaction to produce indazolone, an important heterocycle with biological activity. Faster autocyclization of arylhydrazide is observed when an electron withdrawing group is present in the aryl ring, which is a characteristic of S_NAr reactions.