Scheme 1.

I. Synthesis of triazaphospholes B via the conversion of phosphaalkynes A with organic azides in cycloaddition reactions. II. Synthesis of triazaphospholes D by conversion of the chlorophosphaalkene C with organic azides via TMS–Cl elimination from a cyclic intermediate.^{[ 5 ]} III. Conversion of the 2‐triphenylphosphonium‐1‐chlorophosphaalkene E with phenyl azide, yielding the cationic 5‐phosphonium‐triazaphosphole F.^{[ 6 ].}