Transition metal-free and temperature dependent one-pot access to phenanthrene-fused heterocycles via a 1,3-dipolar cycloaddition pathway

Abstract

A versatile, operationally simple, temperature-dependent, and transition metal-free one-pot protocol has been devised for the preparation of novel phenanthrene-fused pyrazoles. Notably, the overall process involved an intermolecular condensation, an intramolecular 1,3-dipolar cycloaddition, and an aromatization sequence starting from biaryl-2,2′-aldehydes bearing enoate esters with various hydrazine hydrochlorides. Notably, the sequential one-pot three-component operation has also been achieved. Importantly, it was also shown that this protocol was amenable to hydroxylamine hydrochloride as the nitrogen source and furnished phenanthrene-fused isoxazoles. Notably, the temperature dependent nature of this protocol was also demonstrated, which led to the formation of dealkoxylcarbonylated phenanthrene-fused pyrazoles at slightly higher temperatures and longer reaction times. Remarkably, this metal-free protocol effectively constructed two C–N bonds and one C–C bond and exhibited a broad substrate scope.