Synthesis of fully substituted pyrazoles from pyridinium 1,4-zwitterionic thiolates and hydrazonoyl chlorides via a [[3 + 3] − 1] pathway

Abstract

A novel and practical protocol for the synthesis of fully substituted pyrazoles from pyridinium 1,4-zwitterionic thiolates and hydrazonoyl chlorides in excellent yields under mild conditions is described. The transformation proceeds via an unusual [[3 + 3] − 1] pathway, which involves a formal [3 + 3] cascade cyclization followed by a spontaneous ring-contraction/sulfur extrusion reaction from 4H-1,3,4-thiadiazine intermediates.