An unprecedented route to achieve persistent 1 H -azirine.

1 H -azirine, a highly reactive, antiaromatic, and unstable tautomer of the aromatic, stable, and (sometimes) isolable 2 H -azirine, is stabilized, both thermodynamically and kinetically, via an unprecedented route, where the latter serves as the precursor-exploiting electronic and steric elements. Our density functional theory results invite experimentalists to realize isolable 1 H -azirine.