Transformations of
α-EWG-substituted (electron-withdrawing
group, EWG) γ-azidobutyronitriles proceeding via unusual aza-Wittig reactions between the phosphazene and nitrile
functions and affording pyrrole-derived iminophosphazenes were developed.
α-EWGs were found to control chemoselectivity and, depending
on their nature, act as CN group activators (e.g., ester, amide, or
nitrile) or competitors (e.g., ketone) in aza-Wittig
reactions. To demonstrate the synthetic utility of the obtained iminophosphazenes
as N,N-binucleophiles, their transformations
into pyrrole-fused systems, pyrrolo[1,2-a]imidazoles
and pyrrolo[1,2-a][1,3]diazepines,
were carried out.