Frustrated Alternative Approaches towards the Synthesis of a Thermally Stable 1,2-Diazacyclobutene

Abstract

We have previously demonstrated that an appropriately substituted four-membered-ring 1,2-diazacyclobutene is a useful compound in organic synthesis for the introduction of strained 1,2-diazetidine rings. In order to further explore the reactivity of this interesting heterocycle, we sought a method to improve upon the poor synthetic yield reported earlier. A novel route involving the synthesis of a similarly substituted 1,2-diazetidine compound followed by free-radical bromination and base-catalyzed debromination appeared promising. While there are some studies on the synthesis of the desired 1,2-diazetidine precursor, when we attempted its synthesis, we instead observed the exclusive formation of an eight-membered “dimer”-like compound. The structure of this compound was confirmed via single-crystal X-ray analysis. Fortunately, an alternative synthetic approach for the formation of the desired 1,2-diazetidine precursor proved successful, and the structure of the precursor has been confirmed via X-ray analysis. However, unfortunately, the required bromination step proved to be more challenging than expected, and ultimately, this route had to be abandoned since the anticipated improvement upon the original yield did not seem promising. Single-crystal X-ray analysis proved pivotal in properly identifying the structures of the synthesized compounds.