Abstract
5‐Azaindoles either with three different substituents at their 2‐, 4‐, and 6‐positions or with two identical substituents at their 2‐ and 6‐positions and a different one at the 4‐position, were obtained in good to excellent isolated yields by a zirconocene‐mediated multicomponent process. Each reaction involved four organic partners, comprising a Si‐tethered diyne, one __t__BuCN component, and two (either different or identical) nitriles. All these four components were combined through the action of a Cp~2~Zr^II^ species into a three‐ring fused Zr/Si‐containing organometallic complex in a perfectly chemo‐ and regioselective manner. This multicomponent reaction process consisted of three reaction steps, all of which were made clear through the isolation and characterization of their corresponding organometallic intermediates: the zirconacyclopropene‐azasilacyclopentadienes 2, the allenyl‐aza‐zirconacycles 3, and the three‐ring fused complexes 6. X‐ray single‐crystal structural analyses of two three‐ring fused Zr/Si‐containing intermediates and two 5‐azaindoles unambiguously showed the positions of the different substituents and the regioselectivity. Iminopyrrole derivatives could be also highly selectively prepared from a Si‐tethered diyne and two different nitriles.